Amorphous oxide and field effect transistor

ABSTRACT

A novel amorphous oxide applicable, for example, to an active layer of a TFT is provided. The amorphous oxide comprises microcrystals.

The present application is a continuation of Ser. No. 14/806,108, filedon Jul. 22, 2015, which is a continuation of U.S. application Ser. No.13/923,009, filed on Jun. 20, 2013, now issued as U.S. Pat. No.9,130,049, which is a divisional of U.S. application Ser. No.12/406,464, filed on Mar. 18, 2009, which is a divisional of U.S.application Ser. No. 11/269,600, filed on Nov. 9, 2005, now issued asU.S. Pat. No. 7,601,984, which claims priority to JP 2004-326687, filedNov. 10, 2004, the entire disclosure of each of which is incorporated byreference herein.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to an amorphous oxide. The presentinvention also relates to a field effect transistor using an amorphousoxide.

Related Background Art

In recent years, flat panel display (FPD) is commercialized as theresults of progress of liquid crystal techniques, electroluminescence(EL), and the related techniques. The FPD is driven by an active matrixcircuit comprising a field-effect thin film transistor (TFT) employingan amorphous silicon thin film or polycrystalline silicon thin film asthe active layer formed on a glass substrate.

For smaller thickness, lighter weight, and higher impact strength of theFPD, use of a lightweight and a flexible resin substrate is investigatedin place of the glass substrate. However, the transistor employing thesilicon thin film cannot by directly formed on a less heat-resistantresin substrate, since the production of the silicon thin filmtransistor requires a relatively high-temperature in the process,

Therefore, for the TFT, use of an oxide semiconductor thin film such asa ZnO thin film is actively investigated which enables film formation ata lower temperature (Japanese Patent Application Laid-Open No.2003-298062).

However, TFTs using conventional oxide semiconductor thin films have notprovided performances on the same level as of TFTs using silicon.

The present invention relates to an amorphous oxide, and also, to afield effect transistor using the amorphous oxide.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an amorphous oxide foruse in the active layer of a semiconductor device such as a thin filmtransistor (TFT) and serving as a suitable semiconductor, and a fieldeffect transistor.

According to an aspect of the present invention, there is provided aamorphous oxide comprising a microcrystal and having an electron carrierconcentration of less than 10¹⁸/cm³.

The amorphous oxide preferably comprises at least one element selectedfrom the group consisting of In, Zn and Sn.

Alternatively, the amorphous oxide is preferably any one selected fromthe group consisting of an oxide containing In, Zn and Sn; an oxidecontaining In and Zn; an oxide containing In and Sn; and an oxidecontaining In.

Alternatively, the amorphous oxide preferably comprises In, Ga, and Zn.

According to another aspect of the present invention, there is providedan amorphous oxide, wherein electron mobility increases as electroncarrier concentration increases. According to a further aspect of thepresent invention, there is provided a field effective transistorcomprising an active layer formed of an amorphous oxide containing amicrocrystal, and a gate electrode formed so as to face the active layervia a gate insulator.

The transistor is preferably a normally-off type transistor.

According to a still further aspect of the present invention, there isprovided an amorphous oxide whose composition changes in a layerthickness direction and having an electron carrier concentration of lessthan 10¹⁸/cm³.

The amorphous oxide preferably contains at least one element selectedfrom the group consisting of In, Zn and Sn.

Alternatively, the amorphous oxide is preferably any one selected fromthe group consisting of an oxide containing In, Zn and Sn; an oxidecontaining In and Zn; an oxide containing In and Sn; and an oxidecontaining In.

Alternatively, the amorphous oxide preferably contains In, Ga and Zn.

According to a still further aspect of the present invention, there isprovided a field effect transistor comprising

an active layer of an amorphous oxide whose composition changes in alayer thickness direction, and

a gate electrode formed so as to face the active layer via a gateinsulator,

wherein the active layer comprises a first region and a second region,which is closer to the gate insulator than the first region, and theoxygen concentration of the first region is higher than that of thesecond region.

According to a still further aspect of the present invention, there isprovided a field effect transistor comprising

an active layer of an amorphous oxide having at least one elementselected from the group consisting of In and Zn, and

a gate electrode formed so as to face the active layer through a gateinsulator,

wherein the active layer comprises a first region and a second region,which is closer to the gate insulator than the first region, and the Inconcentration of the second region is higher than that of the firstregion, or the Zn concentration of the second region is higher than thatof the first region.

According to a still further aspect of the present invention, there isprovided an amorphous oxide whose composition changes in a layerthickness direction,

wherein electron mobility increases as electron carrier concentrationincreases.

According to a still further aspect of the present invention, there isprovided a field effect transistor comprising

an active layer of an amorphous oxide and having at least one elementselected from the group consisting of In and Zn, and

a gate electrode formed so as to face the active layer via a gateinsulator,

wherein the active layer comprises a first region and a second region,which is closer to the gate insulator than the first region, and the Inconcentration of the second region is higher than that of the firstregion, or the Zn concentration of the second region is higher than thatof the first region.

According to a still further aspect of the present invention, there isprovided an amorphous oxide comprising one type of element or aplurality of types of elements selected from the group consisting of Li,Na, Mn, Ni, Pd, Cu, Cd, C, N, P, Ti, Zr, V, Ru, Ge, Sn, and F and havingan electron carrier concentration of less than 1×10¹⁸/cm³.

The amorphous oxide preferably comprises at least one element selectedfrom the group consisting of In, Zn and Sn.

Alternatively, the amorphous oxide is preferably any one selected fromthe group consisting of an oxide containing In, Zn and Sn; an oxidecontaining In and Zn; an oxide containing In and Sn; and an oxidecontaining In.

Alternatively, the amorphous oxide preferably comprises In, Zn and Ga.

According to a still further aspect of the present invention, there isprovided an amorphous oxide comprising at least one type of elementselected from group consisting of Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, P,Ti, Zr, V, Ru, Ge, Sn, and F, wherein electron mobility increases aselectron carrier concentration increases.

According to a still further aspect of the present invention, there isprovided a field effect transistor comprising

an active layer of an amorphous oxide containing at least one type ofelement selected from the group consisting of Li, Na, Mn, Ni, Pd, Cu,Cd, C, N, P, Ti, Zr, V, Ru, Ge, Sn, and F; and

a gate electrode formed so as to face the active layer via a gateinsulator.

Further, in the present invention, the amorphous oxide is preferablyselected from the group consisting of an oxide containing In, Zn and Sn;an oxide containing In and Zn; an oxide containing In and Sn; and anoxide containing In.

As the results of investigation on the oxide semiconductors by theinventors of the present invention, it was found that theabove-mentioned ZnO is formed in a state of a polycrystalline phase,causing scattering of carriers at the interface between thepolycrystalline grains to lower the electron mobility. Further it wasfound that ZnO is liable to cause oxygen defect therein to produce manycarrier electrons, which makes difficult to lower the electricalconductivity. Thereby, even when a gate voltage is not applied to thetransistor, a large electric current flow is caused between the sourceterminal and the drain terminal, making impossible the normally-offstate of the TFT and a larger on-off ratio of the transistor.

The inventors of the present invention investigated the amorphous oxidefilm Zn_(x)M_(y)In_(z)O_((x+3y/2+3z/2)) (M: at least one element of Aland Ga) mentioned in Japanese Patent Application Laid-Open No.2000-044236. This material contains electron carriers at a concentrationnot less than 1×10¹⁸/cm³, and is suitable as a simple transparentelectrode. However, the oxide containing the electron carrier at aconcentration of not less than 1×10¹⁸/cm³ used in a channel layer of TFTcannot give a sufficient on-off ratio, and is not suitable for thenormally-off TFT. Thus a conventional amorphous oxide film cannotprovide a film of a carrier concentration of less than 1×10¹⁸/cm³.

The inventors of the present invention prepared a TFT by use of anamorphous oxide of a carrier concentration of less than 1×10¹⁸/cm³ as anactive layer of a field-effect transistor. The TFT was found to havedesired properties and to be useful for an image display apparatus likea light emission apparatus.

Further, the inventors of the present invention investigated a materialInGaO₃(ZnO)_(m) and the film forming conditions of this material, andfound that the carrier concentration of this material can be controlledto be less than 1×10¹⁸/cm³ by controlling the oxygen atmosphereconditions in the film formation.

The above explanation is given with a view to a case of using theamorphous oxide as an active layer serving as e.g. a channel layer ofTFT. The present invention is, however, not so limited to the casewherein such an active layer is used.

In the above, mention is mostly made of a case where an amorphous oxideis used as the active layer serving as the channel of a TFT. However,the present invention is not limited to the case.

According to the present invention, there is provided an amorphous oxidethat is suitably used in the channel layer of a transistor, for example,a TFT. The present invention also provides a field effect transistorhaving excellent properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the relationship between the electron carrierconcentration of an In—Ga—Zn—O based amorphous film formed by a pulselaser deposition method and the oxygen partial pressure during filmformation time;

FIG. 2 is a graph showing the relationship between the electricconductivity of an In—Ga—Zn—O based amorphous film formed by asputtering method using argon gas and the oxygen partial pressure duringfilm formation time;

FIG. 3 is a graph showing the relationship between the number ofelectron carriers of an In—Ga—Zn—C based amorphous film formed by apulse laser deposition method and the electron mobility;

FIGS. 4A, 4B and 4C show graphs showing respectively changes of electricconductivity, carrier concentration, and electron mobility versus valuex of a film having a composition of InGaO₃(Zn_(1-x)Mg_(x)O) formed by apulse laser deposition method in an oxygen atmosphere having an oxygenpartial pressure of 0.8 Pa;

FIG. 5 is a schematic illustration showing the structure of a top-gatetype metal insulator semiconductor field effect transistor (MISFET)device;

FIG. 6 is a characteristic graph showing the electric current versusvoltage of a top-gate type MISFET device;

FIG. 7 is a schematic illustration of a film formation apparatusemploying the pulse laser deposition method; and

FIG. 8 is a schematic illustration of a film formation apparatusemploying the sputtering method.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now, the first to third inventions will be explained in accordance withfirst to third embodiments, respectively. After that, an amorphous oxidematerial applicable to the present invention will be explained. In theembodiments below, an In—Ga—Zn—O based oxide will be mainly explained inthe embodiments below; however, the present invention is not limited tosuch material.

First Embodiment: Amorphous Oxide Having a Microcrystals

The invention according to the first embodiment relates to an amorphousoxide, characterized in that the amorphous contains a microcrystal(s).Where a microcrystal(s) are contained or not in the amorphous oxide isdetermined by taking a TEM (transmission electron microscopic)photograph of a section of a formed amorphous oxide film. An amorphousoxide film according to the present invention comprises In—Ga—Zn—O andthe composition of the amorphous oxide film in a crystalline state isrepresented by InGaO₃(ZnO)_(m) (m is a natural number of less than 6).

Oxides represented by the term “amorphous oxide” in the specificationhas an electron carrier concentration is less than 10¹⁸/cm³ or shows atendency that the electron mobility increases as the electron carrierconcentration increases, or and so forth. Although depending on the kindof use of a TFT, it is preferable to use the amorphous TFT forfabricating normally off type TFT.

Alternatively, an amorphous oxide film according to the presentinvention comprises In—Ga—Zn—Mg—O and the composition of the amorphousoxide film in a crystalline state is represented byInGaO₃(Zn_(1-x)Mg_(x)O)_(m) (m is a natural number of less than 6,0<x≤1). It is preferable that these amorphous oxide films have anelectron mobility exceeding 1 cm²/V·sec.

The present inventors found that use of such a film mentioned above as achannel layer makes it possible to form a flexible TFT having transistorcharacteristics: a gate current of less than 0.1 micro ampere when theTFT is off (normally-off) and an on/off ratio exceeding 1×10³, and beingpermeable to visible light.

Such a transparent film is characterized in that the electron mobilityincreases with an increase of the number of conductive electrons. As asubstrate for forming the transparent film, use can be made of a glasssubstrate, plastic substrate and plastic film.

When the transparent oxide film is used as the channel layer of atransistor, it is preferable to employ, as the gate insulator, one typeof compound selected from the group consisting of Al₂O—Y₂O₃ and HfO₂ ora mixed crystal compound containing at least two types selected from thegroup consisting of Al₂O₃, Y₂O₃ and HfO₂.

It is preferable that the film (transparent oxide film) is formed in anatmosphere containing oxygen under light irradiation without addingimpurity ions for enhancing electric resistance on purpose.

<Film Composition>

In a transparent amorphous oxide thin film, which has a composition in acrystalline state represented by InGaO₃(ZnO)_(m) (m is a natural numberof less than 6), the amorphous state can be stably maintained to atemperature as high as 800° C. or more if the value m is less than 6.However, as the value m increases, in other words, the ratio of ZnO toInGaO₃ increases (that is, the composition of the film becomes closer toZnO), the film comes to be easily crystallized

For this reason, it is preferable that the value m is less than 6 whenthe amorphous film is used as the channel layer of an amorphous TFT.However, it is found that when the film is formed under lightirradiation, microcrystals can be formed even though the value m issmall.

The film may be formed by a vapor-phase film formation method with apolycrystalline-sintered body having a composition of InGaO₃(ZnO)_(m)used as a target. Of the vapor-phase film formation methods, asputtering method and a pulse laser deposition method are suitable.Moreover, the sputtering method is most preferable in view oflarge-scale production.

However, such an amorphous film is formed in general conditions, mainlyoxygen defect occurs. Therefore, an electron carrier concentration hasnot yet been reduced to less than 1×10¹⁸/cm³, in other words, 10 S/cm orless in terms of electric conductivity. When such a conventional thinfilm is used, a normally-off transistor cannot be formed. However, whena transparent amorphous oxide film, which has a composition ofIn—Ga—Zn—O and a crystalline state composition represented byInGaO₃(ZnO)_(m) (m is a natural number of less than 6), is formed by apulse laser deposition method using the apparatus shown in FIG. 7, in anatmosphere having a high oxygen partial pressure in excess of 3.2 Pa,the electron carrier concentration can be reduced to less than1×10¹⁸/cm³. In this case, the substrate is not purposely heated andtherefore maintained approximately at room temperature. When a plasticfilm is used as a substrate, the temperature of the plastic film ispreferably maintained at less than 100° C.

According to the invention of this embodiment, an amorphous oxidecomprises In—Ga—Zn—O and formed by a pulse laser deposition method underlight irradiation. More specifically, the invention is directed to atransparent amorphous oxide thin film containing a microcrystal(s)represented by a crystalline state composition of InGaO₃(ZnO)_(m) (m isa natural number of less than 6). A normally-off transistor can beformed by use of such a thin film.

In such a thin film, it is possible to obtain an electron mobilityexceeding 1 cm²/V·sec and a large on/off ratio exceeding 1×10².

Furthermore, the present invention is directed to an amorphous oxidecomprising In—Ga—Zn—O and formed by a sputtering method using argon gasunder light irradiation. More specifically, the present invention isdirected to a transparent amorphous oxide thin film containing amicrocrystal(s) represented by a crystalline state composition,InGaO₃(ZnO)_(m) (m is a natural number of less than 6). Such a film canbe obtained by a sputtering method using the apparatus shown in FIG. 8in an atmosphere having a high oxygen partial pressure in excess of1×10⁻² Pa. In this case, the temperature of the substrate is notpurposely heated and thus maintained approximately at room temperature.When a plastic film is used as a substrate, the substrate temperature ispreferably maintained at less than 100° C. The number of electroncarriers can be reduced by further increasing oxygen partial pressure.

More specifically, the present invention is directed to an amorphousoxide comprising In—Ga—Zn—O prepared by a sputtering deposition methodunder light irradiation. According to the present invention, anormally-off transistor having an on/off ratio exceeding 1×10³ can beformed by using a transparent amorphous oxide thin film containing amicrocrystal(s) represented by a crystalline state composition ofInGaO₃(ZnO)_(m) (m is a natural number of less than 6).

In the thin film prepared by a pulse laser deposition method and asputtering method under light irradiation, the electron mobilityincreases with an increase of the number of conductive electrons.

In this case, if a polycrystalline InGaO₃(Zn_(1-x)Mg_(x)O)_(m) (m is anatural number of less than 6, 0<x≤1) is used as a target, a highresistance amorphous film having a composition ofInGaO₃(Zn_(1-x)Mg_(x)O)_(m) can be obtained even under a partial oxygenpressure of less than 1 Pa.

As explained above, oxygen defect can be overcome by controlling oxygenpartial pressure. As a result, the electron carrier concentration can bereduced without adding predetermined impurity ions. An amorphous oxideaccording to the present invention can be obtained by forming a thinfilm according to any one of FIGS. 1 to 5 under light irradiation. Whenapparatuses according to FIGS. 7 and 8 are used, a film can be formed atan oxygen partial pressure, for example, within the predetermined rangedescribed later. In the amorphous state containing a microcrystal(s),the grain boundary interface of a microcrystal is covered with(surrounded by) an amorphous structure. Therefore, the grain boundaryinterface capable of trapping mobile electrons and holes does notvirtually exist, unlike the polycrystalline state like zinc oxide. As aresult, an amorphous thin film having high electron mobility can beobtained. Furthermore, the number of conductive electrons can be reducedwithout adding predetermined impurity ions. Since electrons are notscattered by the impurity ions, high electron mobility can bemaintained. The microcrystals according to the present invention are notlimited to that having a composition represented by InGaO₃(ZnO)_(m) (mis a natural number of less than 6).

In a thin film transistor employing the transparent film mentionedabove, the gate insulator is preferably formed of a mixed crystalcompound containing at least two compounds selected from the groupconsisting of Al₂O—Y₂O₃ and HfO₂. When a defect (deficiency) is presentin the interface between the gate insulating thin film and the channellayer thin film, the electron mobility decreases and hysteresis as atransistor characteristic, takes place. Furthermore, if the types ofgate insulators differs, leak current greatly varies. For this reason,it is necessary to select a suitable gate insulator for the channellayer. If an Al₂O₃ film is used (as the gate insulator), the leakcurrent can be reduced. If an Y₂O₃ film is used, the hysteresis can bereduced. If an HfO₂ film having a high dielectric constant is used, theelectron mobility can be increased. Furthermore, if a mixed crystal ofthese compounds is used (as a gate insulator), leak current, it ispossible to form a TFT having a small leak current and hysteresis, andlarge electron mobility. Since a gate insulator formation process and achannel layer formation process can be performed at room temperature,not only a stagger-structure TFT but also an inverse-stagger structureTFT may be formed.

A TFT is a device having three terminals, namely, a gate terminal,source terminal and drain terminal. In the TFT, a semiconductor thinfilm formed on an insulating substrate such as ceramic, glass, orplastic substrate is used as a channel layer for migrating electrons andholes therethrough. The current flowing through the channel layer iscontrolled by applying a voltage to the gate terminal, thereby switchingthe current between the source terminal and the drain terminal. Sincethe TFT has such a switching function, it is an active device. Note thatmicrocrystals contained in an amorphous oxide may be formed by lightirradiation (specifically, light irradiation by a halogen lamp or UVirradiation) as mentioned above and may be formed by other methodsexcept for light irradiation.

Second Embodiment: Compositional Distribution of Amorphous Oxide

According to this embodiment, an amorphous oxide is characterized by acomposition varying in a film-thickness direction.

The phrase “composition varying in a film-thickness direction” meansthat the oxygen amount contained in an oxide changes in the filmthickness direction and elements constituting an oxide changes in themiddle (that is, the composition changes), and the contents of theelements constituting an oxide change.

Therefore, when the amorphous oxide is used as the active layer (alsocalled channel layer) of a field effect transistor, for example, thefollowing constitution is preferable. In a transistor having an activelayer containing an amorphous oxide and a gate insulator in contact witheach other at an interface, the amorphous oxide layer is constitutedsuch that the concentration of oxygen near the interface is set higherthan the region away from the interface. In this case, since theelectric resistance of the amorphous oxide layer near the interface ishigh, the so-called channel of the transistor is formed within theamorphous oxide layer away from the interface. Such a constitution ispreferable when the interface is a rough surface, because currentleakage can be reduced.

That is, in case of using the above amorphous oxide as an active layerof the transistor, it is preferable to design the active layer so as tobe comprised of the first region and the second region more adjacent tothe gate insulator than the first region, the concentration of oxygen inthe second region is greater than the that in the first region.Incidentally, the two regions are not necessary to be distinguishable ata boundary of them but may change their respective compositionsgradually or step by step.

In particular, the electron carrier concentration of the amorphous oxideis preferably less than 1¹⁸/cm³.

A direction of the film formed on the substrate means any directionwhich is not in the direction in plane of the substrate, e.g. thedirection perpendicular to the direction in plane of the substrate.Furthermore, in a transistor having an active layer formed of anamorphous oxide having at least one element selected from the groupconsisting of In and Zn and a gate insulator in contact with the activelayer at the interface, the concentration of In or Zn contained in theregion of the amorphous oxide layer (active layer) close to theinterface is higher than the region away from the interface. In thiscase, the electron field-effect mobility can be enhanced.

That is, in case of using the above amorphous oxide as an active layerof the transistor, it is preferable to design the active layer so as tobe comprised of the first region and the second region more adjacent tothe gate insulator than the first region, the concentration of In or Znin the second region is greater than the that in the first region.

According to the second invention, an oxide film comprises In—Ga—Zn—Oand its composition changes in the film-thickness direction, andcharacterized in that the composition of a crystalline-state portion isrepresented by InGaO₃(ZnO)_(m) (m is a natural number of less than 6)and an electron carrier concentration is less than 1×10¹⁸/cm³.

Alternatively, an oxide film according to the second invention is atransparent amorphous oxide film comprising In—Ga—Zn—Mg—O andcharacterized in that the composition changes in a film-thicknessdirection and the composition of a crystalline state portion isrepresented by InGaO₃(Zn_(1-x)Mg_(x)O)_(m) (m is a natural number ofless than 6, 0<x≤1) and an electron carrier concentration is less than1×10¹⁸/cm³. Note that, it is also preferable that these films have anelectron mobility exceeding 1 cm²/V·sec.

When the aforementioned film is used as the channel layer, it ispossible to obtain a flexible TFT having transistor characteristics: agate current of less than 0.1 micro ampere when TFT is off(normally-off), an on/off ratio exceeding 1×10⁴, and being permeable tovisible light.

Note that, such a transparent film is characterized in that the electronmobility increases with an increase of the number of conductiveelectrons. As a substrate for forming the transparent film, use can bemade of a glass substrate, plastic substrate or plastic film.

When the transparent oxide film is used as the channel layer of atransistor, it is preferable to employ one type of compound selectedfrom the group consisting of Al₂O—Y₂O₃ and HfO₂ or a mixed crystalcompound containing at least two types of compounds selected from thegroup consisting of Al₂O₃, Y₂O₃ and HfO₂ as the gate insulator.

It is preferable that the film (transparent oxide film) is formed in anatmosphere containing oxygen without adding impurity ions for enhancingelectric resistance on purpose.

The present inventors found a specific feature of the semi-insulatingamorphous oxide thin film. That is, the electron mobility increases withan increase of the number of conductive electrons. They formed a TFTusing this film and found that the characteristics of the transistor,such as an on/off ratio, saturation current at a pinch-off state, andswitching speed, further increase.

In a film transistor formed by using the transparent semi-insulatingamorphous oxide thin film as the channel layer, when an electronmobility is more than 1 cm²/V·sec, preferably more than 5 cm²/V·sec, andan electron carrier concentration to less than 1×10¹⁸/cm³, preferably,less than 1×10¹⁶/cm³, the current between the drain and source terminalsin the off time (gate voltage is not applied) can be reduced to lessthan 10 micro ampere, preferably, less than 0.1 micro ampere. Further,in this case (of using the aforementioned thin film), when an electronmobility is more than 1 cm²/V·sec, preferably more than 5 cm²/V·sec, thesaturation current after the pinch off can be increased to more than 10micro ampere. In short, an on/off ratio can be increased to more than1×10⁴.

In a TFT, a high voltage is applied to a gate terminal in a pinch offstate, with the result that electrons are present at a high density inthe channel. Therefore, according to the present invention, thesaturation current can be increased by the extent corresponding to anincrease of electron mobility. As a result, almost all characteristicsof the transistor, such as an on/off ratio, saturation current, andswitching rate, are increased and improved. Note that, in a generalcompound, when the number of electrons increases, collision betweenelectrons takes place, with the result that the electron mobilitydecreases.

The amorphous oxide according to the present invention can be used in astaggered (top gate) structure TFT in which the gate insulator and thegate terminal are sequentially formed in this order on the semiconductorchannel layer and in an inverse staggered (bottom gate) structure TFT inwhich the gate insulator and the semiconductor channel layer aresequentially formed in this order on the gate terminal.

<Film Composition>

In a transparent amorphous oxide thin film whose crystalline portion hasa composition represented by InGaO₃(ZnO)_(m) (m is a natural number ofless than 6), when the value m is less than 6, the amorphous state canbe stably maintained to a temperature as high as 800° C. or more.However, as the value m increases, in other words, the ratio of ZnO toInGaO₃ increases (that is, the composition of the film becomes closer toZnO), the film comes to be easily crystallized

For this reason, it is preferable that the value m is less than 6 whenthe amorphous film is used as the channel layer of an amorphous TFT.

A thin film transistor employing the transparent film mentioned abovepreferably uses a gate insulator formed of a mixed crystal compoundcontaining one type of compound selected from the group consisting ofAl₂O₃, Y₂O₃ and HfO₂ or a mixed crystal compound containing at least twotypes of compounds selected from the group consisting of Al₂O₃, Y₂O₃ andHfO₂ When a defect (deficiency) is present in the interface between thegate insulating thin film and the channel layer thin film, the electronmobility decreases and hysteresis as a transistor characteristic, takesplace. Furthermore, if the types of gate insulators differs, leakcurrent greatly varies. For this reason, it is necessary to select asuitable gate insulator for the channel layer. If an Al₂O₃ film is used(as the gate insulator), the leak current can be reduced. If an Y₂O₃film is used, the hysteresis can be reduced. If an HfO₂ film having ahigh dielectric constant is used, the electron mobility can beincreased. Furthermore, if a mixed crystal of these compounds is used(as a gate insulator), leak current, it is possible to form a TFT havinga small leak current and hysteresis, and large electron mobility. Sincea gate insulator formation process and a channel layer formation processcan be performed at room temperature, not only a stagger-structure TFTbut also an inverse-stagger structure TFT may be formed.

A TFT is a device having three terminals, namely, a gate terminal,source terminal and drain terminal. In the TFT, a semiconductor thinfilm formed on an insulating substrate such as ceramic, glass, orplastic substrate is used as a channel layer for migrating electrons andholes therethrough. The current flowing through the channel layer iscontrolled by applying a voltage to the gate terminal, thereby switchingthe current between the source terminal and the drain terminal. Sincethe TFT has such a switching function, it is an active device.

As described above, the second invention is directed to improvement of acomposition in the film thickness direction of the transparent film,which serves as the active layer of a field effect transistor (FET),when the FET is formed using the transparent film.

To explain more specifically, when a pulse laser deposition method isused, a composition is changed in the film-thickness direction byvarying oxygen partial pressure in the film thickness direction, varyingoscillation power of a pulse laser or an oscillation frequency, orvarying the distance between a target and a substrate in the filmthickness direction. On the other hand, when a sputter deposition methodis used, a composition is changed in the film thickness direction byadditionally sputtering a target, such as In₂O₃ or ZnO. For example,when a film is formed under an oxygen atmosphere, the amount of oxygencontained in the film increases as the distance between a target and asubstrate increases. Furthermore, when a ZnO target is added during filmformation time, the amount of Zn increases in the film formed after theaddition of the Zn target.

Third Embodiment: Amorphous Oxide Containing an Additive(s)

An amorphous oxide according to this embodiment is characterized in thatthe amorphous oxide contains at least one or plurality of types ofelements selected from the group consisting of Li, Na, Mn, Ni, Pd, Cu,Cd, C, N, P, Ti, Zr, V, Ru, Ge, Sn, and F are contained as an additive.Introduction of an additive into an amorphous oxide is attained byintroducing the additive in a gas for use in a film formation apparatusor in the film formation apparatus, or in a target material that is usedin the apparatus. As a matter of course, after a film is formed from anamorphous oxide without an additive, the additive may be introduced intothe film as is described later in Examples.

The electron carrier concentration of the amorphos oxide is preferablyless than 10¹⁸/cm³.

An amorphous oxide according to the present invention may include atransparent amorphous oxide comprising In—Ga—Zn—O and whose compositionin a crystalline state is represented by InGaO₃(ZnO)_(m) (m is a naturalnumber of less than 6) and include an oxide comprising In—Ga—Zn—Mg—O andwhose composition in a crystalline state is represented byInGaO₃(Zn_(1-x)Mg_(x)O)_(m) (m is a natural number of less than 6,0<x≤1). To these oxides, further at least one type or plurality of typesof elements selected from the group consisting of Li, Na, Mn, Ni, Pd,Cu, Cd, C, N, and P are introduced as an additive.

In this manner, the electron carrier concentration can be reduced. Eventhough the electron carrier concentration is significantly reduced, itis possible to prevent the electron carrier mobility from decreasing,rendering the control of electron carrier concentration easy. As aresult, when the transparent amorphous oxide film is employed as thechannel layer of a TFT, the resultant TFT panel has a uniformcharacteristic even though the panel has a large area.

When Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, and P, are used as an impurity(additive), these impurities can substitute for any one of In, Ga, Zn, Oand serve as an acceptor and may decrease the electron carrier density,although the details of the mechanism are unknown. In a general oxidesemiconductor, since the oxygen concentration cannot be appropriatelycontrolled, a large number of oxygen deficiencies are produced.Furthermore, mostly in the case where deficiency are produced in thegrain boundary due to a polycrystalline state, the electron carrierdensity cannot be controlled well even if impurities are introduced. Inthis respect, a transparent amorphous oxide film according to thepresent invention has a few oxygen deficiencies and no grain boundarydue to the amorphous state. Hence, it is considered that impuritieseffectively work as the acceptor. When a thin film is formed byincreasing oxygen partial pressure in order to reduce the electroncarrier density, the skeleton of atomic bonding changes, increasing thetail state of the conduction band. If electrons are trapped by the tailstate, the electron carrier mobility may substantially decrease.However, the addition of Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, and P, makesit possible to control the carrier density while maintaining oxygenpartial pressure within an appropriate range. Therefore, the electroncarrier mobility is conceivably less affected. Thus, when the presentinvention is compared to the case where the electron carrierconcentration and the electron carrier mobility are controlled only bycontrolling oxygen partial pressure, the in-plain uniformity ofcharacteristics of an oxide film can be easily enhanced even though alarge substrate is used.

The additive may be selected from the group consisting of Ti, Zr, V, Ru,Ge, Sn and F as mentioned below.

Note that the concentration of impurities required for obtaining adesired effect (in a amorphous film) is about 0.1 to 3 atomic %, whichis higher than that in a crystalline film formed of Si or the like. Thisis considered because the probability that impurity atoms entereffective sites for controlling valence electrons is lower in theamorphous state than on the crystalline state. Most generally, a desiredimpurity is introduced into the target by an impurity introductionmethod. In the case of impurities such as C, N, and P, they can beintroduced into a film by introducing a gas such as CH₄, NO and PH₃together with oxygen to the atmosphere. When a metallic element isintroduced as an impurity, after a transparent amorphous oxide film isformed, the film is brought into contact with a solution or pastecontaining the metallic-element ion. Furthermore, when a substrate suchas a glass having a high heat resistance is used, these metallicelements are previously contained in the substrate and then, thesubstrate is heated during or after the film formation, therebydiffusing the metallic elements into a transparent amorphous oxide film.As a Na source, for example, soda glass can be used since it contains 10to 20 atomic % of Na.

FIG. 5 shows a typical structure of a TFT device. In the TFT device, theportion that can effectively reduce the electron carrier density is thatof a channel layer 2 sandwiched between a drain electrode 5 and a sourceelectrode 6. In contrast, it is advantageous that the portion of thechannel layer 2 in contact with the drain electrode 5 and the sourceelectrode 6 has a high electron carrier density. This is because it canmaintain good contact with the electrodes. In other words, the impurityconcentration of this portion preferably low. Such a constitution can beattained by bringing the channel layer 2 into contact with a solutioncontaining impurities after the drain electrode 5 and the sourceelectrode 6 are formed and before a gate insulting film 3 is formed. Inthis manner, the impurities can be diffused with the drain electrode 5and the source electrode 6 used as a mask.

In FIG. 5, the portion of the channel layer 2 especially in contact withthe substrate is not easily placed under the control of the gateelectrode 4 for electron carrier density. Therefore, it is helpful ifthe electron carrier density of the portion is previously suppressedlow, in order to increase the on/off ratio. Then, it is effective toincrease the concentration of impurities particularly at the interfacefacing the substrate. Such a constitution can be attained by controllingthe concentration of a gas such as CH₄, NO and PH₃ to be introduced intothe atmosphere, in such a manner that the gas is started to supply at anexcessive concentration and gradually reduced in concentration.Alternatively, in the case of an impurity such as Na previouslycontained in a substrate, such a constitution can be attained bydiffusing Na by heating the substrate at an appropriate temperature.

As an additive, at least one type or a plurality of types of elementsselected from the group consisting of Ti, Zr, V, Ru, Ge, Sn, and F maybe introduced into an amorphous oxide. In this case, it is expected thatthe electron mobility can be increased to 1 cm²/V·sec or more, andfurther to 5 cm²/V·sec or more while keeping an electron carrierconcentration of less than 1×10¹⁸/cm². Even if the electron field-effectmobility increases, the electron carrier concentration rarely increasesin accordance therewith. Hence, when the transparent amorphous oxidefilm is used as the channel layer, it is possible to obtain a TFT havinga high on/off ratio and a large saturation current during the pinch offtime as well as a high switching speed. Furthermore, it is easy toenhance the in-plane uniformity of oxide-film characteristics even if alarge substrate is used, compared to the case where the electron carrierconcentration and the electron carrier mobility are controlled only byadjusting oxygen partial pressure.

Although details of the mechanism are unknown, when an oxide is formedby increasing the partial oxygen pressure, the tail state density of aportion under a conduction band increases, with the result that themobility may decrease. However, impurities such as Ti, Zr, V, Ru, Ge,Sn, and F, conceivably act on the skeleton of atomic bonding, therebyreducing the tail state, with the result that the electron carriermobility can be enhanced while maintaining the electron carrier density.

These impurities mentioned above are preferably used in a concentrationwithin the range of about 0.1 to 3 atomic % or 0.01 to 1 atomic %. Theterm “atomic %” is a ratio of the atomic number of a constitutionalelement contained in an oxide. Note that when it is difficult to measurethe amount of oxygen, the aforementioned ranges may be defined by aratio of the atomic numbers of constitutional elements except foroxygen. Most generally, a desired impurity is introduced into the targetby a method of introducing an impurity. In the case of an impurity of F,it can be introduced into a film by introducing a gas such as SF₆, SiF₄,or CLF₃ together with oxygen to the atmosphere. When a metallic elementis introduced as the impurity, after a transparent amorphous oxide filmis formed, the film is brought into contact with a solution or pastecontaining the metallic-element ion.

FIG. 5 shows a typical structure of a TFT device. In the TFT device, theportion in which especially high electron mobility is required, is thatof the channel layer 2 in contact with the gate insulator 3. Then, it iseffective that the impurity concentration of the present invention isincreased particularly in the interface in contact with the gateinsulation film 3. Such a constitution can be attained by introducing agas such as SF₆, SiF₄, and CLF₃ into an atmosphere during the channellayer formation time while increasing the concentration of the gas(starting from a lower level).

In the present invention, it is basically important that atomic bondingstructure can be appropriately formed by controlling the amount ofoxygen (oxygen defect amount).

In the aforementioned description, the amount of oxygen in a transparentoxide film is controlled by forming a film in an atmosphere containing apredetermined amount of oxygen. It is also preferable that after anoxide film is formed, it is treated in an atmosphere containing oxygen,thereby controlling (decreasing or increasing) the oxygen defect amount.

To effectively control the oxygen defect amount, a film is treated in anatmosphere containing oxygen set at a temperature from 0 to 300° C.(both inclusive), preferably from 25 to 250° C. (both inclusive),further preferable 100 to 200° C. (both inclusive).

As a matter of course, not only film formation but also treatment afterthe film formation may be performed in an atmosphere containing oxygen.Furthermore, as long as a predetermined electron carrier concentration(less than 1×10¹⁸/cm³) is obtained, a film may be formed withoutcontrolling oxygen partial pressure and thereafter the film may betreated in an atmosphere containing oxygen.

In the present invention, the lowermost electron carrier concentrationvaries depending upon the use of the obtained oxide film, morespecifically, the type of device, circuit, and apparatus; however, forexample, 1×10¹⁴/cm³ or more is preferable.

Now, amorphous oxides applicable to Embodiments 1 to 3 will be describedin detail below. To the amorphous oxides or the manufacturing methodsthereof, the following conditions are added. In the invention accordingto the first embodiment, light irradiation is added to the manufacturingconditions. In the invention according to the second embodiment, meansfor changing a film composition are used as described in Examples. Inthe invention according to the third embodiment, in addition to the filmformation conditions, a gas and a target for adding impurities are usedor, after the film formation, a predetermined method for addingimpurities to amorphous oxide shown below may be employed.

(Amorphous Oxide)

The active layer employed in the above Embodiments 1 to 3 of theinvention is explained below.

The electron carrier concentration in the amorphous oxide in the presentinvention is a value measured at a room temperature. The roomtemperature is a temperature in the range from 0° C. to about 40° C.,for example, 25° C. The electron carrier concentration in the amorphousoxide in the present invention need not be less than 10¹⁸/cm³ throughoutthe entire range from 0 to 40° C. For example, the electron carrierconcentration of less than 1×10¹⁸/cm³ at a temperature of 25° C. isacceptable. At a lower electron carrier concentration, not more than1×10¹⁷/cm³, or not more than 1×10¹⁶/cm³, a normally-off TFT can beproduced at a high yield.

In the present specification, the description “less than 10¹⁸/cm³”means—preferably less than 1×10¹⁸/cm³ and more preferably less than1.0×10¹⁸/cm³−.

The electron carrier concentration can be measured by measurement of aHall Effect.

The amorphous oxide in the present invention is an oxide which exhibitsa halo pattern and no characteristic diffraction line in an X-raydiffraction spectrometry.

In the amorphous oxide of the present invention, the lower limit of theelectron carrier concentration is, for example, 1×10¹²/cm³, but is notlimited insofar as it is applicable as a channel layer of a TFT.

Accordingly, in the present invention, the electron carrierconcentration is adjusted by controlling the material, compositionratio, production conditions, and so forth of the amorphous oxide as inthe Examples described later to be in the range, for instance, from1×10¹²/cm³ to 1×10¹⁸/cm³, preferably from 1×10¹³/cm³ to 1×10¹⁷/cm³, morepreferably from 1×10¹⁵/cm³ to 1×10¹⁶/cm³.

The amorphous oxide, other than the InZnGa oxides, can be selectedsuitably from In oxides, In_(x)Zn_(1-x) oxides (0.2≤x≤1), In_(x)Sn_(1-x)oxides (0.8≤x≤1), and In_(x)(Zn,Sn)_(1-x) oxides (0.15≤x≤1). TheIn_(x)(Zn,Sn)_(1-x) oxide can also be represented byIn_(x)(Zn_(y)Sn_(1-y))_(1-x) (0≤x≤1).

When the In oxide contains neither Zn nor Sn, the In can be partlysubstituted by Ga: In_(x)Ga_(1-x) oxide (0≤x≤1).

An amorphous oxide of an electron carrier concentration of 1×10¹⁸/cm³which is prepared by the inventors of the present invention is describedbelow in detail.

One group of the aforementioned oxides are characteristicallyconstituted of In—Ga—Zn—O, represented by InGaO₃(ZnO)_(m) (m: a naturalnumber of less than 6) in a crystal state, and containing electroncarriers at a concentration of less than 1×10¹⁸/cm³.

The other group of the aforementioned oxides are characteristicallyconstituted of In—Ga—Zn—Mg—O, represented by InGaO₃(Zn_(1-x)Mg_(x)O)_(m)(m: a natural number of less than 6, and 0<x·1) in a crystal state, andcontaining electron carriers at a concentration of less than 1×10¹⁸/cm³.

The film constituted of such an oxide is preferably designed to exhibitpreferably an electron mobility of higher than 1 cm²/V·sec.

By use of the above film as the channel layer, a TFT can be preparedwhich is normally-off with a gate current of less than 0.1 microamperein a transistor off-state, having an on-off ratio of higher than 1×10³,being transparent to visible light and flexible.

In the above film, the electron mobility increases with the increase ofthe conduction electrons. The substrate for forming the transparent filmincludes glass plates, plastic plates, and plastic films.

In using the above amorphous oxide film as the channel layer, at leastone of layers constituted of Al₂O₃, Y₂O₃ or HfO₂, or a mixed crystalcompound thereof is useful as the gate insulator.

In a preferred embodiment, the film is formed in an oxygengas-containing atmosphere without intentional addition of an impurityfor increasing the electric resistance to the amorphous oxide.

The inventors of the present invention found that the amorphous thinfilms of semi-insulating oxides have characteristics that the electronmobility therein increases with increase in number of conductionelectrons, and further found that a TFT prepared by use of the film isimproved in transistor characteristics such as the on-off ratio, thesaturation current in a pinch-off state, and the switching rate. Thus anormally-off type TFT can be produced by use of the amorphous oxide.

By use of the amorphous oxide thin film as the channel layer of a filmtransistor, the electron mobility can be made higher than 1 cm²/V·sec,preferably higher than 5 cm²/V·sec. The current between the drainterminal and the source terminal at an off-state (no gate voltageapplied) can be controlled to be less than 10 microamperes, preferablyless than more than 0.1 microamperes at the carrier concentration oflower than 1×10¹⁸/cm³, preferably lower than 1×10¹⁶/cm³. Further by useof this thin film, the saturation current after pinch-off can be raisedto 10 microamperes or more and the on-off ratio can be raised to behigher than 1×10³ for the electron mobility higher than 1 cm²/V·sec,preferably higher than 5 cm²/V·sec.

In a pinch-off state of the TFT, a high voltage is being applied to thegate terminal, and electrons are existing in a high density in thechannel. Therefore, according to the present invention, the saturationcurrent can be increased in correspondence with the increase of theelectron mobility. Thereby, the transistor characteristics can beimproved, such as increase of the on-off ratio, increase of thesaturation current, and increase of the switching rate. In contrast, ina usual compound, the increase of electrons decreases the electronmobility owing to collision between electrons.

The structure of the aforementioned TFT may be a stagger (top gate)structure in which a gate insulator and a gate terminal are successivelyformed on a semiconductor channel layer, or a reversed stagger (bottomgate) structure in which a gate insulator and a semiconductor channellayer successively on a gate terminal.

(First Process for Film Formation: PLD Process)

The amorphous oxide thin film having the composition InGaO₃(ZnO)_(m) (m:a natural number of less than 6) in a crystal state is stable up to ahigh temperature of 800° C. or higher when m is less than 6, whereaswith increase of m, namely with increase of the ratio of ZnO to InGaO₃near to the composition of ZnO, the oxide tends to crystallize.Therefore, the value m of the oxide is preferably less than 6 for use asthe channel layer of the amorphous TFT.

The film formation is conducted preferably by a gas phase film formationprocess by use of a target of a polycrystalline sintered compact havinga composition InGaO₃(ZnO)_(m). Of the gas phase film formationprocesses, sputtering, and pulse laser vapor deposition are suitable.The sputtering is particularly suitable for the mass-production.

However, in formation of the amorphous film under usual conditions,oxygen defect can occur, so that the electron carrier concentration ofless than 1×10¹⁸/cm³ and electric conductivity of less the 10 S/cmcannot be achieved. With such a film, a normally-off transistor cannotbe constituted.

The inventors of the present invention produced an In—Ga—Zn—O film by apulse laser vapor deposition by use of the apparatus shown in FIG. 7.

The film-forming was carried out by using such a PLD film-formingapparatus as shown in FIG. 7.

In FIG. 7, the numerals indicate the followings: 701, an RP (rotarypump); 702, a TMP (turbo molecular pump); 703, a preliminary chamber;704, an electron gun for RHEED; 705, a substrate-holding means forrotating and vertically moving the substrate; 706, a laser-introducingwindow; 707, a substrate; 708, a target; 709, a radical source; 710, agas inlet; 711, a target-holding means for rotating and verticallymoving the target; 712, a by-pass line; 713, a main line; 714, a TMP(turbo molecular pump); 715, an RP (rotary pump); 716, a titanium getterpump; 717, a shutter; 718, an IG (ion manometer); 719, a PG (Piranigage); 720, a BG (baratron gage); and 721, a growth chamber.

An In—Ga—Zn—O type amorphous oxide semiconductor thin film was depositedon an SiO₂ glass substrate (Corning Co.: 1737) by a pulse laser vapordeposition employing a KrF excimer laser. As the pretreatment before thedeposition, the substrate was washed ultrasonically for defatting withacetone, ethanol, and ultrapure water each for five minutes, and driedin the air at 100° C.

The polycrystalline target was an InGaO₃(ZnO)₄ sintered compact (size:20 mm diameter, 5 mm thick), which had been prepared by wet-mixingIn₂O₃, Ga₂O₃, and ZnO (each 4N reagent) as the source material (solvent:ethanol), calcining the mixture (1000° C., 2 hours), dry-crushing it,and sintering it (1550° C., 2 hours). The target had an electroconductivity of 90 S/cm.

The film formation was conducted by controlling the final vacuum of thegrowth chamber to be 2×10⁻⁶ Pa, and the oxygen partial pressure duringthe growth to be 6.5 Pa. The oxygen partial pressure in growth chamber721 was 6.5 Pa, and the substrate temperature was 25° C. The distancebetween target 708 and film-holding substrate 707 was 30 mm, the powerintroduced through introduction window 716 was in the range of 1.5-3mJ/cm²/pulse. The pulse width was 20 nsec, the repeating frequency was10 Hz, and the irradiation spot size was 1×1 mm square. Under the aboveconditions, the film was formed at a rate of 7 nm/min.

The resulting thin film was examined by small angle X-ray scatteringmethod (SAXS) (thin film method, incidence angle: 0.5°): no cleardiffraction peak was observed. Thus the obtained In—Ga—Zn—O type thinfilm was judged to be amorphous. From X-ray reflectivity and its patternanalysis, the mean square roughness (Rrms) was found to be about 0.5 nm,and the film thickness to be about 120 nm. From fluorescence X-rayspectrometric analysis (XRF), the metal composition of the film wasfound to be In:Ga:Zn=0.98:1.02:4. The electric conductivity was lessthan about 1×10⁻² S/cm. The electron carrier concentration was estimatedto be not more than 1×10⁻¹⁶/cm². The electron mobility was estimated tobe about 5 cm²/V·sec. From light absorption spectrum analysis, theoptical band gap energy breadth of the resulting amorphous thin film wasestimated to be about 3 eV.

The above results show that the obtained In—Ga—Zn—O type thin film is atransparent flat thin film having an amorphous phase of a compositionnear to a crystalline InGaO₃(ZnO)₄, having less oxygen defect, andhaving lower electric conductivity.

The above film formation is explained specifically by reference toFIG. 1. FIG. 1 shows dependency of the electron carrier concentration inthe formed transparent amorphous oxide thin film on the oxygen partialpressure for the film of a composition of InGaO₃(ZnO)_(m) (m: an integerless than 6) in an assumed crystalline state under the same filmformation conditions as in the above Example.

By formation of the film in an atmosphere having an oxygen partialpressure of higher than 4.5 Pa under the same conditions as in the aboveExample, the electron carrier concentration could be lowered to lessthan 1×10¹⁸/cm³ as shown in FIG. 1. In this film formation, thesubstrate was kept nearly at room temperature without intentionalheating. For use of a flexible plastic film as the substrate, thesubstrate temperature is kept preferably at a temperature lower than100° C.

The higher oxygen partial pressure enables decrease of the electroncarrier concentration. For instance, as shown in FIG. 1, the thinInGaO₃(ZnO)₄ film formed at the substrate temperature of 25° C. and theoxygen partial pressure of 5 Pa had a lower electron carrierconcentration of 1×10¹⁶/cm³.

In the obtained thin film, the electron mobility was higher than 1cm²/V·sec as shown in FIG. 2. However, the film deposited by the pulselaser vapor deposition at an oxygen partial pressure of higher than 6.5Pa as in this Example has a rough surface, being not suitable for achannel layer of the TFT.

Accordingly, a normally-off type transistor can be constructed by usinga transparent thin amorphous oxide represented by InGaO₃(ZnO)_(m) (m: anumber less than 6) in a crystal state formed at an oxygen partialpressure of higher than 4.5 Pa, preferably higher than 5 Pa, but lowerthan 6.5 Pa by a pulse laser vapor deposition method in the aboveExample. The above obtained thin film exhibited an electron mobilityhigher than 1 cm²/V, and the on-off ratio could be made higher than1×10³.

As described above, in formation of an InGaZn oxide film by a PLD methodunder the conditions shown in this Example, the oxygen partial pressureis controlled in the range preferably from 4.5 Pa to 6.5 Pa.

For achieving the electron carrier concentration of 1×10¹⁸/cm³, theoxygen partial pressure conditions, the constitution of the filmformation apparatus, the kind and composition of the film-formingmaterial should be controlled.

Next, a top-gate type MISFET element as shown in FIG. 5 was produced byforming an amorphous oxide with the aforementioned apparatus at anoxygen partial pressure of 6.5 Pa. Specifically, on glass substrate 1, asemi-insulating amorphous InGaO₃(ZnO)₄ film of 120 nm thick was formedfor use for channel layer 2 by the above method of formation ofamorphous thin Ga—Ga—Zn—O film. Further thereon an InGaO₃(ZnO)₄ filmhaving a higher electro conductivity and a gold film were laminatedrespectively in a thickness of 30 nm by pulse laser deposition at anoxygen partial pressure of lower than 1 Pa in the chamber. Then drainterminal 5 and source terminal 6 were formed by photolithography and alift-off method. Finally, a Y₂O₃ film for gate insulator 3 was formed byan electron beam vapor deposition method (thickness: 90 nm, relativedielectric constant: about 15, leak current density: 1×10⁻³ A/cm³ atapplication of 0.5 MV/cm). Thereon, a gold film was formed, and gateterminal 4 was formed by photolithography and lifting-off.

Evaluation of Characteristics of MISFET Element

FIG. 6 shows current-voltage characteristics of the MISFET elementmeasured at room temperature. The channel is understood to be an n-typesemiconductor from the increase of the drain current I_(DS) with theincrease of the drain voltage V_(DS). This is consistent with the factthat an amorphous In—Ga—Zn—O type semiconductor is of an n-type. TheI_(DS) becomes saturated (pinched off) at V_(DS)=6V, which is typicalbehavior of a semiconductor transistor. From examination of the gaincharacteristics, the threshold value of the gate voltage V_(DS) underapplication of V_(DS)=4V was found to be about −0.5 V. A current flow ofI_(DS)=1.0×10⁻⁵ A was caused at V_(G)=10V. This corresponds to carrierinduction by gate bias in the In—Ga—Zn—O type amorphous semiconductorthin film.

The on-off ratio of the transistor was higher than 1×10³. From theoutput characteristics, the field effect mobility was calculated to beabout 7 cm²(Vs)⁻¹. Irradiation of visible light did not change thetransistor characteristics of the produced element according to the samemeasurement.

According to the present invention, a thin film transistor can beproduced which has a channel layer containing electron carriers at alower concentration to achieve higher electric resistance and exhibitinga higher electron mobility.

The above amorphous oxide has excellent characteristics that theelectron mobility increases with the increase of the electron carrierconcentration, and exhibits degenerate conduction. In this Example, thethin film was formed on a glass substrate. However, a plastic plate orfilm is useful as the substrate since the film formation can beconducted at room temperature. Further, the amorphous oxide obtained inthis Example, absorbs visible light only little to give transparentflexible TFT.

(Second Process for Film Formation: Sputtering Process (SP Process))

Film formation by a high-frequency SP process by use of an argon gas asthe atmosphere gas is explained below.

The SP process was conducted by use of the apparatus shown in FIG. 8. InFIG. 8, the numerals indicates the followings: 807, a substrate for filmformation; 808, a target; 805, a substrate-holding means equipped with acooling mechanism; 814, a turbo molecular pump; 815, a rotary pump; 817,a shutter; 818, an ion manometer; 819, a Pirani gage; 821, a growthchamber; and 830, a gate valve.

Substrate 807 for film formation was an SiO₂ glass substrate (CorningCo.: 1737) which had been washed ultrasonically for defatting withacetone, ethanol, and ultrapure water respectively for 5 minutes, anddried at 100° C. in the air.

The target was a polycrystalline sintered compact having a compositionof InGaO₃(ZnO)₄ (size: 20 nm diameter, 5 mm thick), which had beenprepared by wet-mixing In₂O₃, Ga₂O₃, and ZnO (each 4N reagent) as thesource material (solvent: ethanol), calcining the mixture (1000° C., 2hours), dry-crushing it, and sintering (1550° C., 2 hours). Target 808had an electro conductivity of 90 S/cm, being semi-insulating.

The final vacuum degree of growth chamber 821 was 1×10⁻⁴ Pa. During thegrowth, the total pressure of the oxygen and argon gas was kept constantwithin the range of 4 to 0.1×10⁻¹ Pa. The partial pressure ratio ofargon to oxygen was changed in the range of the oxygen partial pressurefrom 1×10⁻³ to 2×10⁻¹ Pa.

The substrate temperature was room temperature. The distance betweentarget 808 and substrate 807 for film formation was 30 mm.

The inputted electric power was RF 180 W, and the film forming rate was10 nm/min.

The resulting thin film was examined by small angle X-ray scatteringmethod (SAXS) (thin film method, incidence angle: 0.5°): no cleardiffraction peak was observed. Thus the obtained In—Ga—Zn—O type thinfilm was judged to be amorphous. From X-ray reflectivity and its patternanalysis, the mean square roughness (Rrms) was found to be about 0.5 nm,and the film thickness to be about 120 nm. From fluorescence X-rayspectrometric analysis (XRF), the metal composition of the film wasfound to be In:Ga:Zn=0.98:1.02:4.

The films were formed at various oxygen partial pressure of theatmosphere, and the resulting amorphous oxide films were measured forelectric conductivity. FIG. 3 shows the result.

As shown in FIG. 3, the electric conductivity can be lowered to lessthan 10 S/cm by conducting the film formation in an atmosphere having anoxygen partial pressure higher then 3×10⁻² Pa. The electron carriernumber could be decreased by increase of the oxygen partial pressure.

As shown in FIG. 3, for instance, the thin InGaO₃(ZnO)₄ film formed atthe substrate temperature of 25° C. and the oxygen partial pressure or1×10⁻¹ Pa had a lower electric conductivity of about 1×10⁻¹⁰ S/cm.Further, the thin InGaO₃(ZnO)₄ film formed at the oxygen partialpressure or 1×10⁻¹ Pa had an excessively high electric resistance,having the electric conductivity not measurable. With this film,although the electron mobility was not measurable, the electron mobilitywas estimated to be about 1 cm²/V·sec by extrapolation from the valuesof the films of high electron carrier concentration.

Thus, a normally-off transistor having the on-off ratio of higher than1×10³ could be obtained by use of a transparent thin amorphous oxidefilm constituted of In—Ga—Zn—O represented in a crystal state byInGaO₃(ZnO)_(m) (m: a natural number of less than 6) produced bysputtering vapor deposition in an argon atmosphere containing oxygen ata partial pressure of higher than 3×10⁻² Pa, preferably higher than5×10⁻¹ Pa.

In use of the apparatus and the material employed in this Example, thefilm formation by sputtering is conducted in the oxygen partial pressureranging from 3×10⁻² Pa to 5×10⁻¹ Pa. Incidentally, in the thin filmproduced by pulse laser vapor deposition or sputtering, the electronmobility increases with increase in number of the conductive electrons.

As described above, by controlling the oxygen partial pressure, theoxygen defect can be decreased, and thereby the electron carrierconcentration can be decreased. In the amorphous thin film, the electronmobility can be high, since no grain interface exists essentially in theamorphous state differently from polycrystalline state.

Incidentally, the substitution of the glass substrate by a 200 μm-thickpolyethylene terephthalate (PET) film did not change the properties ofthe amorphous oxide film of InGaO₃(ZnO)₄ formed thereon.

A high-resistance amorphous film InGaO₃(Zn_(1-x)Mg_(x)O)_(m) (m: annatural number less than 6; 0<x·1) can be obtained by using, as thetarget, polycrystalline InGaO₃(Zn_(1-x)Mg_(x)O)_(m) even at an oxygenpartial pressure less than 1 Pa. For instance, with a target in which 80atom % of Zn is replaced by Mg, the electron carrier concentration lowerthan 1×10¹⁶/cm (resistance: about 1×10⁻² S/cm) can be achieved by pulselaser deposition in an atmosphere containing oxygen at a partialpressure of 0.8 Pa. In such a film, the electron mobility is lower thanthat of the Mg-free film, but the decrease is slight: the electronmobility is about 5 cm²/V·sec at room temperature, being higher by aboutone digit than that of amorphous silicon. When the films are formedunder the same conditions, increase of the Mg content decreases both theelectric conductivity and the electron mobility. Therefore, the contentof the Mg ranges preferably from 20% to 85% (0.2<x<0.85).

In the thin film transistor employing the above amorphous oxide film,the gate insulator contains preferably a mixed crystal compoundcontaining two or more of Al₂O₃, Y₂O₃, HfO₂, and compounds thereof.

The presence of a defect at the interface between the gate-insulatingthin film and the channel layer thin film lowers the electron mobilityand causes hysteresis of the transistor characteristics. Moreover, thecurrent leakage depends greatly on the kind of the gate insulator.Therefore the gate insulator should be selected to be suitable for thechannel layer. The current leakage can be decreased by use of an Al₂O₃film, the hysteresis can be made smaller by use of a Y₂O₃ film, and theelectron mobility can be increased by use of an HfO₂ film having a highdielectric constant. By use of the mixed crystal of the above compounds,TFT can be formed which causes smaller current leakage, less hysteresis,and exhibiting a higher electron mobility. Since the gate insulatorforming process and the channel layer forming process can be conductedat room temperature, the TFT can be formed in a stagger constitution orin a reversed stagger constitution.

The TFT thus formed is a three-terminal element having a gate terminal,a source terminal, and a drain terminal. This TFT is formed by forming asemiconductor thin film on a insulating substrate of a ceramics, glass,or plastics as a channel layer for transport of electrons or holes, andserves as an active element having a function of controlling the currentflowing through the channel layer by application of a voltage to thegate terminal, and switching the current between the source terminal andthe drain terminal.

In the present invention, it is important that an intended electroncarrier concentration is achieved by controlling the amount of theoxygen defect.

In the above description, the amount of the oxygen in the amorphousoxide film is controlled by controlling the oxygen concentration in thefilm-forming atmosphere. Otherwise the oxygen defect quantity can becontrolled (decreased or increase) by post-treatment of the oxide filmin an oxygen-containing atmosphere as a preferred embodiment.

For effective control of the oxygen defect quantity, the temperature ofthe oxygen-containing atmosphere is controlled in the range from 0° C.to 300° C., preferably from 25° C. to 250° C., more preferably from 100°C. to 200° C.

Naturally, a film may be formed in an oxygen-containing atmosphere andfurther post-treated in an oxygen-containing atmosphere. Otherwise thefilm is formed without control of the oxygen partial pressure andpost-treatment is conducted in an oxygen-containing atmosphere, insofaras the intended electron carrier concentration (less than 1×10¹⁸/cm³)can be achieved.

The lower limit of the electron carrier concentration in the presentinvention is, for example, 1×10¹⁴/cm % depending on the kind of theelement, circuit, or device employing the produced oxide film.

(Broader Range of Materials)

After investigation on other materials for the system, it was found thatan amorphous oxide composed of at least one oxide of the elements of Zn,In, and Sn is useful for an amorphous oxide film of a low carrierconcentration and high electron mobility.

This amorphous oxide film was found to have a specific property thatincrease in number of conductive electrons therein increases theelectron mobility. Using this film, a normally-off type TFT can beproduced which is excellent in transistor properties such as the on-offratio, the saturation current in the pinch-off state, and the switchingrate.

In the present invention, an oxide having any one of the characteristicsof (a) to (h) below are useful:

(a) An amorphous oxide which has an electron carrier concentration lessthan 1×10¹⁸/cm²;

(b) An amorphous oxide in which the electron mobility becomes increasedwith increase of the electron carrier concentration;

(The room temperature signifies a temperature in the range from about 0°C. to about 40° C. The term “amorphous compound” signifies a compoundwhich shows a halo pattern only without showing a characteristicdiffraction pattern in X-ray diffraction spectrum. The electron mobilitysignifies the one measured by the Hall effect.)(c) An amorphous oxide mentioned in the above items (a) or (b), in whichthe electron mobility at room temperature is higher than 0.1 cm²/V·sec;(d) An amorphous oxide mentioned, in any of the items (b) to (c), whichshows degenerate conduction; (The term “degenerate conduction” signifiesthe state in which the thermal activation energy in temperaturedependency of the electric resistance is not higher than 30 meV.)(e) An amorphous oxide, mentioned in any of the above item (a) to (d),which contains at least one of the elements of Zn, In, and Sn as theconstituting element;(f) An amorphous oxide film composed of the amorphous oxide mentionedthe above item (e), and additionally at least one of the elements ofGroup-2 elements M2 having an atomic number lower than Zn (Mg, and Ca),Group-3 elements M3 having an atomic number lower than In (B, Al, Ga,and Y),Group-4 elements M4 having an atomic number lower than Sn (Si, Ge, andZr),Group-5 elements M5 (V, Nb, and Ta), and Lu, and W to lower the electroncarrier concentration;(g) An amorphous oxide film, mentioned in any of the above items (a) to(f), constituted of a single compound having a composition ofIn_(1-x)M3_(x)O₃(Zn_(1-y)M2_(y)O)_(m) (0≤x≤1; 0≤y≤1; m: 0 or a naturalnumber of less than 6) in a crystal state, or a mixture of the compoundsdifferent in number m, an example of M3 being Ga, and an example of M2being Mg; and(h) An amorphous oxide film, mentioned in any of the above items (a) to(g) formed on a plastic substrate or an plastic film.

The present invention also provides a field-effect transistor employingthe above mentioned amorphous oxide or amorphous oxide film as thechannel layer.

A field-effect transistor is prepared which is employs an amorphousoxide film having an electron carrier concentration of less than1×10¹⁸/cm³ but more than 1×10¹⁵/cm³ as the channel layer, and having asource terminal and a drain terminal, and a gate terminal withinterposition of a gate insulator. When a voltage of about 5 V isapplied between the source and drain terminals without application ofgate voltage, the electric current between the source and drainterminals is about 1×10⁻⁷ amperes.

The electron mobility in the oxide crystal becomes larger with increaseof the overlap of the s-orbitals of the metal ions. In an oxide crystalof Zn, In, or Sn having a higher atomic number, the electron mobility isin the range from 0.1 to 200 cm²/V·sec.

In an oxide, oxygen and metal ions are bonded by ionic bonds withoutorientation of the chemical bonds, having a random structure. Thereforein the oxide in an amorphous state, the electron mobility can becomparable to that in a crystal state.

On the other hand, substitution of the Zn, In, or Sn with an element ofa lower atomic number decreases the electron mobility. Thereby theelectron mobility in the amorphous oxide of the present invention rangesfrom about 0.01 to 20 cm²/V·sec.

In the transistor having a channel layer constituted of the above oxide,the gate insulator is preferably formed from Al₂O₃, Y₂O₃, HfO₂, or amixed crystal compound containing two or more thereof.

The presence of a defect at the interface between the gate-insulatingthin film and the thin channel layer film lowers the electron mobilityand causes hysteresis of the transistor characteristics. Moreover, thecurrent leakage depends greatly on the kind of the gate insulator.Therefore the gate insulator should be selected to be suitable for thechannel layer. The current leakage can be decreased by use of an Al₂O₃film, the hysteresis can be made smaller by use of a Y₂O₃ film, and theelectron mobility can be increased by use of an HfO₂ film having a highdielectric constant. By use of the mixed crystal of the above compounds,TFT can be formed which causes smaller current leakage, less hysteresis,and exhibiting a higher electron mobility. Since the gateinsulator-forming process and the channel layer-forming process can beconducted at room temperature, the TFT can be formed in a staggerconstitution or in a reversed stagger constitution.

The In₂O₃ oxide film can be formed through a gas-phase process, andaddition of moisture in a partial pressure of about 0.1 Pa to thefilm-forming atmosphere makes the formed film amorphous.

ZnO and SnO₂ respectively cannot readily be formed in an amorphous filmstate. For formation of the ZnO film in an amorphous state, In₂O₃ isadded in an amount of 20 atom %. For formation of the SnO₂ film in anamorphous state, In₂O₃ is added in an amount of 90 atom %. In formationof Sn—In—O type amorphous film, gaseous nitrogen is introduced in apartial pressure of about 0.1 Pa in the film formation atmosphere.

To the above amorphous film, may be added an element capable of forminga complex oxide, selected from Group-2 elements M2 having an atomicnumber lower than Zn (Mg, and Ca), Group-3 elements M3 having an atomicnumber lower than In (B, Al, Ga, and Y), Group-4 elements M4 having anatomic number lower than Sn (Si, Ge, and Zr), Group-5 elements M5 (V,Nb, and Ta), and Lu, and W. The addition of the above element stabilizesthe amorphous film at room temperature, and broadens the compositionrange for amorphous film formation.

In particular, addition of B, Si, or Ge tending to form a covalent bondis effective for amorphous phase stabilization. Addition of a complexoxide constituted of ions having largely different ion radiuses iseffective for amorphous phase stabilization. For instance, in an In—Zn—Osystem, for formation of a film stable at room temperature, In should becontained more than about 20 atom %. However, addition of Mg in anamount equivalent to In enables formation of stable amorphous film inthe composition range of In of not less than about 15 atom %.

In a gas-phase film formation, an amorphous oxide film of the electroncarrier concentration ranging from 1×10¹⁵/cm³ to 1×10¹⁸/cm³ can beobtained by controlling the film forming atmosphere.

An amorphous oxide film can be suitably formed by a vapor phase processsuch as a pulse laser vapor deposition process (PLD process), asputtering process (SP process), and an electron-beam vapor deposition.Of the vapor phase processes, the PLD process is suitable in view ofease of material composition control, whereas the SP process is suitablein view of the mass production. However, the film-forming process is notlimited thereto.

(Formation of In—Zn—Ga—O Type Amorphous Oxide Film by PLD Process)

An In—Zn—Ga—O type amorphous oxide was deposited on a glass substrate(Corning Co.: 1737) by a PLD process employing a KrF excimer laser witha polycrystal sintered compact as the target having a composition ofInGaO₃(ZnO) or InGaO₃(ZnO)₄.

The apparatus shown in FIG. 7 was employed which is mentioned before,and the film formation conditions were the same as mentioned before forthe apparatus.

The substrate temperature was 25° C.

The resulting two thin films were examined by small angle X-rayscattering method (SAXS) (thin film method, incidence angle: 0.5°): noclear diffraction peak was observed, which shows that the obtainedIn—Ga—Zn—O type thin films produced with two different targets were bothamorphous.

From X-ray reflectivity of the In—Zn—Ga—O type amorphous oxide film ofthe glass substrate and its pattern analysis, the mean squareroughnesses (Rrms) of the thin films were found to be about 0.5 nm, andthe film thicknesses to be about 120 nm. From fluorescence X-rayspectrometric analysis (XRF), the film obtained with the target of thepolycrystalline sintered compact of InGaO₃(ZnO) was found to contain themetals at a composition ratio In:Ga:Zn=1.1:1.1:0.9, whereas the filmobtained with the target of the polycrystalline sintered compact ofInGaO₃(ZnO)₄ was found to contain the metals at a composition ratioIn:Ga:Zn=0.98:1.02:4.

Amorphous oxide films were formed at various oxygen partial pressure ofthe film-forming atmosphere with the target having the composition ofInGaO₃(ZnO)₄. The formed amorphous oxide films were measured for theelectron carrier concentration. FIG. 1 shows the results. By formationof the film in an atmosphere having an oxygen partial pressure of higherthan 4.2 Pa, the electron carrier concentration could be lowered to lessthan 1×10¹⁸/cm³ as shown in FIG. 1. In this film formation, thesubstrate was kept nearly at room temperature without intentionalheating. At the oxygen partial pressure of lower than 6.5 Pa, thesurfaces of the obtained amorphous oxide films were flat.

At the oxygen partial pressure of 5 Pa, in the amorphous film formedwith the InGaO₃(ZnO)₄ target, the electron carrier concentration was1×10¹⁶/cm³, the electro conductivity was 1×10⁻² S/cm, and the electronmobility therein was estimated to be about 5 cm²/V·sec. From theanalysis of the light absorption spectrum, the optical band gap energybreadth of the formed amorphous oxide film was estimated to be about 3eV.

The higher oxygen partial pressure further lowered the electron carrierconcentration. As shown in FIG. 1, in the In—Zn—Ga—O type amorphousoxide film formed at a substrate temperature of 25° C. at an oxygenpartial pressure of 6 Pa, the electron carrier concentration was loweredto 8×10¹⁵/cm³ (electroconductivity: about 8×10⁻³ S/cm). The electronmobility in the film was estimated to be 1 cm²/V·sec or more. However,by the PLD process, at the oxygen partial pressure of 6.5 Pa or higher,the deposited film has a rough surface, being not suitable for use asthe channel layer of the TFT.

The In—Zn—Ga—O type amorphous oxide films were formed at various oxygenpartial pressures in the film-forming atmosphere with the targetconstituted of a polycrystalline sintered compact having the compositionof InGaO₃(ZnO)₄. The resulting films were examined for the relationbetween the electron carrier concentration and the electron mobility.FIG. 2 shows the results. Corresponding to the increase of the electroncarrier concentration from 1×10¹⁶/cm² to 1×10²⁰/cm², the electronmobility increased from about 3 cm²/V·sec to about 11 cm²/V·sec. Thesame tendency was observed with the amorphous oxide films obtained withthe polycrystalline sintered InGaO₃(ZnO) target.

The In—Zn—Ga—O type amorphous oxide film which was formed on a 200μm-thick polyethylene terephthalate (PET) film in place of the glasssubstrate had similar characteristics.

(Formation of In—Zn—Ga—Mg—O Type Amorphous Oxide Film by PLD Process)

A film of InGaO₃(Zn_(1-x)Mg_(x)O)₄ (0<x·1) was formed on a glasssubstrate by a PLD process with an InGaO₃(Zn_(1-x)Mg_(x)O)₄ target(0<x·1). The apparatus employed was the one shown in FIG. 7.

An SiO₂ glass substrate (Corning Co.: 1737) was used as the substrate.As the pretreatment, the substrate was washed ultrasonically fordefatting with acetone, ethanol, and ultrapure water each for fiveminutes, and dried in the air at 100° C. The target was a sinteredcompact of InGaO₃(Zn_(1-x)Mg_(x)O)₄ (x=1−0) (size: 20 mm diameter, 5 mmthick).

The target was prepared by wet-mixing source materials In₂O₃, Ga₂O₃, andZnO (each 4N reagent) (solvent: ethanol), calcining the mixture (1000°C., 2 hours), dry-crushing it, and sintering it (1550° C., 2 hours). Thefinal pressure in the growth chamber was 2×10⁻⁶ Pa. The oxygen partialpressure during the growth was controlled at 0.8 Pa. The substratetemperature was room temperature (25° C.). The distance between thetarget and the substrate for film formation was 30 mm. The KrF excimerlaser was irradiated at a power of 1.5 mJ/cm²/pulse with the pulse widthof 20 nsec, the repeating frequency of 10 Hz, and the irradiation spotsize of 1×1 mm square. The film-forming rate was 7 nm/min. The oxygenpartial pressure in the film-forming atmosphere was 0.8 Pa. Thesubstrate temperature was 25° C.

The resulting thin film was examined by small angle X-ray scatteringmethod (SAXS) (thin film method, incidence angle: 0.5°): no cleardiffraction peak was observed. Thus the obtained In—Ga—Zn—Mg—O type thinfilm was amorphous. The resulting film had a flat surface.

By using targets of different x-values (different Mg content),In—Zn—Ga—Mg—O type amorphous oxide films were formed at the oxygenpartial pressure of 0.8 Pa in a film-forming atmosphere to investigatethe dependency of the conductivity, the electron carrier concentration,and the electron mobility on the x-value.

FIGS. 4A, 4B, and 4C show the results. At the x values higher than 0.4,in the amorphous oxide films formed by the PLD process at the oxygenpartial pressure of 0.8 Pa in the atmosphere, the electron carrierconcentration was decreased to be less than 1×10¹⁸/cm³. In the amorphousfilm of x value higher than 0.4, the electron mobility was higher than 1cm²/V.

As shown in FIGS. 4A, 4B, and 4C, the electron carrier concentrationless than 1×10¹⁶/cm³ could be achieved in the film prepared by a pulselaser deposition process with the target in which 80 atom % of Zn isreplaced by Mg and at the oxygen partial pressure of 0.8 Pa (electricresistance: about 1×10⁻² S·cm). In such a film, the electron mobility isdecreased in comparison with the Mg-free film, but the decrease isslight. The electron mobility in the films is about 5 cm²/V·sec, whichis higher by about one digit than that of amorphous silicon. Under thesame film formation conditions, both the electric conductivity and theelectron mobility in the film decrease with increase of the Mg content.Therefore, the Mg content in the film is preferably more than 20 atom %and less than 85 atom % (0.2<x<0.85), more preferably 0.5<x<0.85.

The amorphous film of InGaO₂(Zn_(1-x)Mg_(x)O)₄ (0<x·1) formed on a 200μm-thick polyethylene terephthalate (PET) film in place of the glasssubstrate had similar characteristics.

(Formation of In₂O₃ Amorphous Oxide Film by PLD Process)

An In₂O₃ film was formed on a 200 μm-thick PET film by use of a targetconstituted of In₂O₃ polycrystalline sintered compact by a PLD processemploying a KrF excimer laser.

The apparatus used is shown in FIG. 7. The substrate for the filmformation was an SiO₂ glass substrate (Corning Co.: 1737).

As the pretreatment before the deposition, the substrate was washedultrasonically for defatting with acetone, ethanol, and ultrapure watereach for five minutes, and dried in the air at 100° C.

The target was an In₂O₃ sintered compact (size: 20 mm diameter, 5 mmthick), which had been prepared by calcining the source material In₂O₃(4N reagent) (1000° C., 2 hours), dry-crushing it, and sintering it(1550° C., 2 hours).

The final vacuum of the growth chamber was 2×10⁶ Pa, the oxygen partialpressure during the growth was 5 Pa, and the substrate temperature was25° C.

The water vapor partial pressure was 0.1 Pa, and oxygen radicals weregenerated by the oxygen radical-generating assembly by application of200 W.

The distance between the target and the film-holding substrate was 40mm, the power of the Krf excimer laser was 0.5 mJ/cm²/pulse, the pulsewidth was 20 nsec, the repeating frequency was 10 Hz, and theirradiation spot size was 1×1 mm square.

The film-forming rate was of 3 nm/min.

The resulting thin film was examined by small angle X-ray scatteringmethod (SAXS) (thin film method, incidence angle: 0.5°): no cleardiffraction peak was observed, which shows that the obtained In—O typeoxide film was amorphous. The film thickness was 80 nm.

In the obtained In—O type amorphous oxide film, the electron carrierconcentration was 5×10¹⁷/cm³, and the electron mobility was about 7cm²/V·sec.

(Formation of In—Sn—O Type Amorphous Oxide Film by PLD Process)

An In—Sn—O type oxide film was formed on a 200 μm-thick PET film by useof a target constituted of polycrystalline sintered compact of(In_(0.9)Sn_(0.1))O_(3.1) by a PLD process employing a KrF excimerlaser. The apparatus used is shown in FIG. 7.

The substrate for the film formation was an SiO₂ glass substrate(Corning Co.: 1737).

As the pretreatment before the deposition, the substrate was washedultrasonically for defatting with acetone, ethanol, and ultrapure watereach for five minutes, and dried in the air at 100° C.

The target was an In₂O₃—SnO₂ sintered compact (size: 20 mm diameter, 5mm thick), which had been prepared by wet-mixing the source materialsIn₂O₃—SnO₂ (4N reagents) (solvent: ethanol), calcining the mixture(1000° C., 2 hours), dry-crushing it, and sintering it (1550° C., 2hours).

The substrate was kept at room temperature. The oxygen partial pressurewas 5 Pa. The nitrogen partial pressure was 0.1 Pa. Oxygen radicals weregenerated by the oxygen radical-generating assembly by application of200 W.

The distance between the target and the film-holding substrate was 30mm, the power of the Krf excimer laser was 1.5 mJ/cm²/pulse, the pulsewidth was 20 nsec, the repeating frequency was 10 Hz, and theirradiation spot size was 1×1 mm square.

The film-forming rate was of 6 nm/min.

The resulting thin film was examined by small angle X-ray scatteringmethod (SAXS) (thin film method, incidence angle: 0.5°): no cleardiffraction peak was detected, which shows that the obtained In—Sn—Otype oxide film is amorphous.

In the obtained In—Sn—O type amorphous oxide film, the electron carrierconcentration was 8×10¹⁷/cm³, and the electron mobility was about 5cm²/V·sec. The film thickness was 100 nm.

(Formation of In—Ga—O Type Amorphous Oxide Film by PLD Process)

The substrate for the film was an SiO₂ glass substrate (Corning Co.:1737).

As the pretreatment before the deposition, the substrate was washedultrasonically for defatting with acetone, ethanol, and ultrapure watereach for five minutes, and dried in the air at 100° C.

The target was a sintered compact of (In₂O₃)_(1-x)—(Ga₂O₃)_(x) (x=0-1)(size: 20 mm diameter, 5 mm thick). For instance, at x=0.1, the targetis a polycrystalline sintered compact of (In_(0.9)Ga_(0.1))₂O₂.

This target was prepared by wet-mixing the source materials In₂O₃—Ga₂O₂(4N reagents) (solvent: ethanol), calcining the mixture (1000° C., 2hours), dry-crushing it, and sintering it (1550° C., 2 hours).

The final pressure of the growth chamber was 2×10⁻⁶ Pa. The oxygenpartial pressure during the growth was 1 Pa.

The substrate was at room temperature. The distance between the targetand the film-holding substrate was 30 mm. The power of the Krf excimerlaser was 1.5 mJ/cm²/pulse. The pulse width was 20 nsec. The repeatingfrequency was 10 Hz. The irradiation spot size was 1×1 mm square. Thefilm-forming rate was of 6 nm/min.

The substrate temperature was 25° C. The oxygen pressure was 1 Pa. Theresulting film was examined by small angle X-ray scattering method(SAXS) (thin film method, incidence angle: 0.5°): no clear diffractionpeak was detected, which shows that the obtained In—Ga—O type oxide filmis amorphous. The film thickness was 120 nm.

In the obtained In—Ga—O type amorphous oxide film, the electron carrierconcentration was 8×10¹⁶/cm², and the electron mobility was about 1cm²/V·sec.

(Preparation of TFT Element Having In—Zn—Ga—O Type Amorphous Oxide Film(Glass Substrate))

A top gate type TFT element shown in FIG. 5 was prepared.

Firstly, an In—Ga—Zn—O type amorphous oxide film was prepared on glasssubstrate 1 by the aforementioned PLS apparatus with a targetconstituted of a polycrystalline sintered compact having a compositionof InGaO₃(ZnO)₄ at an oxygen partial pressure of 5 Pa. The formedIn—Ga—Zn—O film had a thickness of 120 nm, and was used as channel layer2.

Further thereon, another In—Ga—Zn—O type amorphous film having a higherelectro conductivity and a gold layer were laminated, each in 30 nmthick, by the PLD method at the oxygen partial pressure of lower than 1Pa in the chamber. Therefrom drain terminal 5 and source terminal 6 wereformed by photolithography and a lift-off method.

Finally, a Y₂O₃ film as gate insulator 3 was formed by electron beamvapor deposition (thickness: 90 nm, relative dielectric constant: about15, leakage current density: 1×10³ A/cm² under application of 0.5MV/cm). Further thereon, a gold film was formed and therefrom gateterminal 4 was formed by photolithography and a lift-off method. Thechannel length was 50 μm, and the channel width was 200 μm.

Evaluation of Characteristics of TFT Element

FIG. 6 shows current-voltage characteristics of the TFT element at roomtemperature. Drain current I_(DS) increased with increase of drainvoltage V_(DS), which shows that the channel is of an n-type conduction.

This is consistent with the fact that an amorphous In—Ga—Zn—O typesemiconductor is of an n-type. The I_(DS) become saturated (pinched off)at V_(DS)=6V, which is typical behavior of a semiconductor transistor.From examination of the gain characteristics, the threshold value of thegate voltage V_(GS) under application of V_(DS)=4V was found to be about−0.5 V. A current flow of I_(DS)=1.0×10⁻⁵ A was cased at V_(G)=10V. Thiscorresponds to carrier induction by a gate bias in the In—Ga—Zn—O typeamorphous semiconductor thin film as the insulator.

The on-off ratio of the transistor was higher than 1×10³. From theoutput characteristics, the field effect mobility was calculated to beabout 7 cm²(Vs)⁻¹ in the saturation region. Irradiation of visible lightdid not change the transistor characteristics of the produced elementaccording to the same measurement.

The amorphous oxide of the electron carrier concentration lower than1×10¹⁸/cm³ is useful as a channel layer of a TFT. The electron carrierconcentration is more preferably less than 1×10¹⁷/cm³, still morepreferably less than 1×10¹⁶/cm³.

(Preparation of TFT Element Having In—Zn—Ga—O Type Amorphous Oxide Film(Amorphous Substrate))

A top gate type TFT element shown in FIG. 5 was prepared.

Firstly, an In—Ga—Zn—O type amorphous oxide film was prepared onpolyethylene terephthalate (PET) film 1 by the aforementioned PLSapparatus with a target constituted of a polycrystalline sinteredcompact having a composition of InGaO₃(ZnO) at an oxygen partialpressure of 5 Pa in the atmosphere. The formed film had a thickness of120 nm, and was used as channel layer 2.

Further thereon, another In—Ga—Zn—O type amorphous film having a higherelectro conductivity and a gold layer were laminated, each in 30 nmthick, by the PLD method at the oxygen partial pressure of lower than 1Pa in the chamber. Therefrom drain terminal 5 and source terminal 6 wereformed by photolithography and a lift-off method.

Finally, gate insulator 3 was formed by an electron beam vapordeposition method. Further thereon, a gold film was formed and therefromgate terminal 4 was formed by photolithography and a lift-off method.The channel length was 50 μm, and the channel width was 200 μm. ThreeTFTs of the above structure were prepared by using respectively one ofthe three kinds of gate insulators: Y₂O₃ (140 nm thick), Al₂O₃ (130 μmthick), and HfO₂ (140 μm thick). Evaluation of Characteristics of TFTElement

The TFT elements formed on a PET film had current-voltagecharacteristics similar to that shown in FIG. 6 at room temperature.Drain current I_(DS) increased with increase of drain voltage V_(DS),which shows that the channel is of an n-type conduction. This isconsistent with the fact that an amorphous In—Ga—Zn—O type semiconductoris of an n type. The I_(DS) become saturated (pinched off) at V_(DS)=6V,which is typical behavior of a semiconductor transistor. A current flowof I_(DS)=1.0×10⁻⁸ A was caused at V_(G)=0 V, and a current flow ofI_(DS)=2.0×10⁻⁵ A was caused at V_(G)=10 V. This corresponds to carrierinduction by gate bias in the insulator, the In—Ga—Zn—O type amorphoussemiconductor oxide film.

The on-off ratio of the transistor was higher than 1×10³. From theoutput characteristics, the field effect mobility was calculated to beabout 7 cm²(Vs)⁻¹ in the saturation region.

The elements formed on the PET film were curved at a curvature radius of30 mm, and in this state, transistor characteristics were measured.However the no change was observed in the transistor characteristics.Irradiation of visible light did not change the transistorcharacteristics.

The TFT employing the Al₂O₃ film as the gate insulator has alsotransistor characteristics similar to that shown in FIG. 6. A currentflow of I_(DS)=1.0×10⁻⁸ A was caused at V_(G)=0 V, and a current flow ofI_(DS)=5.0×10⁻⁶ A was caused at V_(G)=10 V. The on-off ratio of thetransistor was higher than 1×10². From the output characteristics, thefield effect mobility was calculated to be about 2 cm²(Vs)⁻¹ in thesaturation region.

The TFT employing the HfO₂ film as the gate insulator has alsotransistor characteristics similar to that shown in FIG. 6. A currentflow of I_(DS)=1×10⁻⁸ A was caused at V_(G)=0 V, and a current flow ofI_(DS)=1.0×10⁻⁶ A was caused at V_(G)=10 V. The on-off ratio of thetransistor was higher than 1×10². From the output characteristics, thefield effect mobility was calculated to be about 10 cm²(Vs)⁻¹ in thesaturation region.

(Preparation of TFT Element Employing In₂O₃ Amorphous Oxide Film by PLDProcess)

A top gate type TFT element shown in FIG. 5 was prepared.

Firstly, an In₂O₃ type amorphous oxide film was formed on polyethyleneterephthalate (PET) film 1 by the PLD method as channel layer 2 in athickness of 80 nm.

Further thereon, another In₂O₃ amorphous film having a higher electroconductivity and a gold layer were laminated, each in 30 nm thick, bythe PLD method at the oxygen partial pressure of lower than 1 Pa in thechamber, and at the voltage application of zero volt to the oxygenradical generating assembly. Therefrom drain terminal 5 and sourceterminal 6 were formed by photolithography and a lift-off method.

Finally, a Y₂O₃ film as gate insulator 3 was formed by an electron beamvapor deposition method. Further thereon, a gold film was formed andtherefrom gate terminal 4 was formed by photolithography and a lift-offmethod.

Evaluation of Characteristics of TFT Element

The TFT elements formed on a PET film was examined for current-voltagecharacteristics at room temperature. Drain current I_(DS) increased withincrease of drain voltage V_(DS), which shows that the channel is ann-type conductor. This is consistent with the fact that an amorphousIn—O type amorphous oxide film is an n type conductor. The I_(DS) becomesaturated (pinched off) at about V_(DS)=6 V, which is typical behaviorof a transistor. A current flow of I_(DS)=2×10⁻⁸ A was caused at V_(G)=0V, and a current flow of I_(DS)=2.0×10⁻⁶ A was caused at V_(G)=10 V.This corresponds to electron carrier induction by gate bias in theinsulator, the In—O type amorphous oxide film.

The on-off ratio of the transistor was about 1×10². From the outputcharacteristics, the field effect mobility was calculated to be about1×10 cm²(Vs)⁻¹ in the saturation region. The TFT element formed on aglass substrate had similar characteristics.

The elements formed on the PET film were curved in a curvature radius of30 mm, and in this state, transistor characteristics were measured. Nochange was observed in the transistor characteristics.

(Preparation of TFT Element Employing In—Sn—O Type Amorphous Oxide Filmby PLD Process)

A top gate type TFT element shown in FIG. 5 was prepared.

Firstly, an In—Sn—O type amorphous oxide film was formed in a thicknessof 100 nm as channel layer 2 on polyethylene terephthalate (PET) film 1by the PLD method.

Further thereon, another In—Sn—O amorphous film having a higher electroconductivity and a gold layer were laminated, each in 30 nm thick, bythe PLD method at the oxygen partial pressure lower than 1 Pa in thechamber, and at voltage application of zero volt to the oxygen radicalgenerating assembly. Therefrom drain terminal 5 and source terminal 6were formed by photolithography and a lift-off method.

Finally, a Y₂O₃ film as gate insulator 3 was formed by an electron beamvapor deposition method. Further thereon, a gold film was formed andtherefrom gate terminal 4 was formed by photolithography and a lift-offmethod.

Evaluation of Characteristics of TFT Element

The TFT elements formed on a PET film was examined for current-voltagecharacteristics at room temperature. Drain current I_(DS) increased withincrease of drain voltage V_(DS), which shows that the channel is ann-type conductor. This is consistent with the fact that an amorphousIn—Sn—O type amorphous oxide film is an n type conductor. The I_(DS)became saturated (pinched off) at about V_(DS)=6 V, which is typicalbehavior of a transistor. A current flow of I_(DS)=5×10⁻⁸ A was causedat V_(G)=0 V, and a current flow of I_(DS)=5.0×10⁻⁵ A was caused atV_(G)=10 V. This corresponds to electron carrier induction by the gatebias in the insulator, the In—Sn—O type amorphous oxide film.

The on-off ratio of the transistor was about 1×10³. From the outputcharacteristics, the field effect mobility was calculated to be about 5cm²(Vs)⁻¹ in the saturation range. The TFT element formed on a glasssubstrate had similar characteristics.

The elements formed on the PET film were curved at a curvature radius of30 mm, and in this state, transistor characteristics were measured. Nochange was caused thereby in the transistor characteristics.

(Preparation of TFT Element Employing In—Ga—O Type Amorphous Oxide Filmby PLD Process)

A top gate type TFT element shown in FIG. 5 was prepared.

Firstly, an In—Ga—O type amorphous oxide film was formed in a thicknessof 120 nm as channel layer 2 on polyethylene terephthalate (PET) film 1by the PLD method shown in Example 6.

Further thereon, another In—Ga—O amorphous film having a higherconductivity and a gold layer were laminated, each in 30 nm thick, bythe PLD method at the oxygen partial pressure of lower than 1 Pa in thechamber, and at the voltage application of zero volt to the oxygenradical-generating assembly. Therefrom drain terminal 5 and sourceterminal 6 were formed by photolithography and a lift-off method.

Finally, a Y₂O₃ film as gate insulator 3 was formed by an electron beamvapor deposition method. Further thereon, a gold film was formed andtherefrom gate terminal 4 was formed by photolithography and a lift-offmethod.

Evaluation of Characteristics of TFT Element

The TFT elements formed on a PET film was examined for current-voltagecharacteristics at room temperature. Drain current I_(DS) increased withincrease of drain voltage V_(DS), which shows that the channel is ann-type conductor. This is consistent with the fact that an amorphousIn—Ga—O type amorphous oxide film is an n type conductor. The I_(DS)became saturated (pinched off) at about V_(DS)=6 V, which is typicalbehavior of a transistor. A current flow of I_(DS)=1×10⁻⁸ A was causedat V_(G)=0 V, and a current flow of I_(DS)=1.0×10⁻⁶ A was caused atV_(G)=10 V. This corresponds to electron carrier induction by the gatebias in the insulator, the In—Ga—O type amorphous oxide film.

The on-off ratio of the transistor was about 1×10². From the outputcharacteristics, the field effect mobility was calculated to be about0.8 cm²(Vs)⁻¹ in the saturation range. The TFT element formed on a glasssubstrate had similar characteristics.

The elements formed on the PET film were curved at a curvature radius of30 mm, and in this state, transistor characteristics were measured. Nochange was caused thereby in the transistor characteristics.

The amorphous oxide of the electron carrier concentration of lower than1×10¹⁸/cm³ is useful as the channel layer of the TFT. The electroncarrier concentration is more preferably not higher than 1×10¹⁷/cm³,still more preferably not higher than 1×10¹⁶/cm³.

Now, Examples of the present invention will be explained.

Example 1: Preparation of an Amorphous In—Ga—Zn—O Thin Film ContainingMicrocrystals

A film is prepared by using the apparatus shown in FIG. 7. A pulse laserdeposition method using KrF excimer laser is performed with apolycrystalline sintered body having a composition of InGaO₃(ZnO)₄ as atarget. On a glass substrate (1737, manufactured by CorningIncorporated), an In—Ga—Zn—O based amorphous oxide semiconductor thinfilm containing microcrystals is deposited. In the film formation step,a substrate surface is irradiated with a halogen lamp (20 mW/cm²). Thepresence or absence of microcrystals is confirmed under TEM(transmission electron microscope) observation of a film section.

<Preparation of MISFET (Metal Insulator Semiconductor Field EffectTransistor) Device>

A top-gate type MISFET device shown in FIG. 5 is manufactured. First, asemi-insulating amorphous InGaO₃(ZnO)₄ film of 30 nm in thicknesscontaining microcrystals and serving as a channel layer (2) is formed onthe glass substrate (1) in accordance with the aforementioned method forpreparing an amorphous In—Ga—Zn—O thin film containing microcrystals.Further on the resultant construct, InGaO₃(ZnO)₄ film and a gold filmlarge in electric conductivity, each having 30 nm thickness, are stackedby a pulse laser deposition method while setting the oxygen partialpressure of a chamber at less than 1 Pa. Then, a drain terminal (5) anda source terminal (6) are formed by a photolithographic method and alift-off method. Finally, an Y₂O₃ film serving as a gate insulator (3)is formed by an electron beam deposition method (the obtained film has athickness of 90 to 110 nm, a specific dielectric constant of about 15,leak current density of 1×10³ A/cm² when a current of 0.5 MV/cm isapplied). Thereafter, a gold film is formed on the resultant construct,and then, a gate terminal (4) is formed by a photolithographic methodand a lift-off method. In this manner, the field effect transistor isformed.

The on/off ratio of the transistor exceeds 1×10⁴. When the field effectmobility is calculated based on power characteristics, an electronfield-effect mobility of about 7.5 cm²(Vs)⁻¹ was obtained in asaturation field. The device thus manufactured was irradiated withvisible light and subjected to the same measurement. As a result, anychange in the characteristics of a transistor was not observed.

Furthermore, in the aforementioned Example for manufacturing anIn—Ga—Zn—O thin film containing microcrystals, effective results areobtained when the substrate is irradiated with light having a powerdensity of 0.3 mW/cm² to 100 mW/cm². As a result, the on/off ratio ofthe transistor can be increased and large electron field-effect mobilitycan be obtained. For this reason, light irradiation is preferable.Although it varies depending upon the amount of microcrystals in anamorphous oxide film, the presence of microcrystals is generallyconfirmed if a peak is detected by X-ray diffraction.

Example 2: Preparation of an Amorphous In—Ga—Zn—O Thin Film Having aCompositional Distribution in the Film Thickness Direction

An In—Ga—Zn—O based amorphous oxide semiconductor thin film having acompositional distribution in the film thickness direction is depositedon a glass substrate (1737, manufactured by Corning Incorporated) by apulse laser deposition method using KrF excimer laser with apolycrystalline sintered body having a composition of InGaO₃(ZnO)₄ as atarget. The film is deposited in a chamber having inner oxygen partialpressure within a predetermined range while increasing the distancebetween the target and the substrate up to 5 mm. As the distanceincreases, the amount of oxygen incorporated into the formed filmincreases. Note that the temperature of the substrate is set at 25° C.

In the Example 2 (for forming a thin film having a compositionaldistribution in the film thickness direction), a composition may bechanged by varying oxygen partial pressure in the film thicknessdirection, or alternatively, by changing an oscillation power oroscillation frequency of a pulse laser. In this manner, leak current canbe reduced or the on/off ratio of a transistor can be increased, as wellas electron field-effect mobility can be increased.

Example 3: Preparation of an Amorphous In—Ga—Zn—O Thin Film Having aCompositional Distribution in the Film Thickness Direction

The film is formed by a sputtering method using argon gas. As targets,(1) a polycrystalline sintered body having a composition of InGaO₃(ZnO)₄and (2) a zinc oxide sintered body are prepared. Then, an amorphousIn—Ga—Zn—O thin film having a compositional distribution in the filmthickness direction is deposited on a glass substrate (1737,manufactured by Corning Incorporated). The film is formed by thesputtering method in an atmosphere having a predetermined oxygen partialpressure, first by using target (1), subsequently by using target (1)and target (2), simultaneously. In this manner, the amorphous In—Ga—Zn—Othin film having a compositional distribution in the film thicknessdirection can be prepared. Note that the temperature of the substrate isset at 25° C.

The In—Ga—Zn—O thin film having a compositional distribution in the filmthickness direction may be prepared by the following manner. Thecomposition is distributed in the film thickness direction by sputteringan In₂O₃ target simultaneously or separately, or changing oxygen partialpressure in the film thickness direction, or alternatively, changingpower supply in the film thickness direction for each target in asputtering step. Particularly, in the amorphous thin film near a gateinsulator, electron field-effect mobility is expected to increase as theamount of In₂O₃ or ZnO increases.

Example 4: Preparation of Amorphous In—Ga—Zn—O(N) Thin Film

A method of preparing an amorphous oxide containing nitrogen (N) as anadditive will be explained.

An In—Ga—Zn—O based amorphous oxide semiconductor thin film containingnitrogen as an impurity (simply referred to as “In—Ga—Zn—O(N)”) isdeposited on a glass substrate of the same type as above by a pulselaser deposition method using KrF excimer laser with an InGaO₃(ZnO)₄polycrystalline sintered body used as a target. Note that the oxygenpartial pressure within a chamber is set at, for example, 4 Pa, thenitrogen partial pressure is set at 1 Pa, and the temperature of asubstrate is set at 25° C. The compositional ratio of oxygen andnitrogen of the thin film is preferably about 50:1, as analyzed by asecondary ion mass spectrum (SIMS).

Example 5: Preparation of Amorphous In—Ga—Zn—O(Ti) Thin Film

An In—Ga—Zn—O based amorphous oxide semiconductor thin film is depositedon a glass substrate (1737, manufactured by Corning Incorporated) by apulse laser deposition method using KrF excimer laser with apolycrystalline sintered body having a composition of InGaO₃(ZnO)₄ usedas a target. The resultant In—Ga—Zn—O based thin film is soaked in anaqueous solution of titanium trichloride kept at 80° C. Thereafter, thefilm is taken up and annealed at 300° C. in the air. In this manner, Tican be introduced as an impurity in the amorphous oxide. As the Ticoncentration of the thin film is analyzed from the surface to thebottom by SIMS, the Ti concentration of the outermost surface is about0.5% and gradually decreases toward the bottom.

An amorphous oxide according to the present invention is applicable tothe channel layer of a transistor. Such a transistor can be used asswitching devices for LCDs and organic EL displays. Alternatively, theamorphous oxide may be applied on a flexible material such as a plasticfilm to form a semiconductor thin film. Such a semiconductor thin filmcan be widely used as panels of flexible displays, IC cards and ID tags.

This application claims priority from Japanese Patent Application No.2004-326687 filed on Nov. 10, 2004, which is hereby incorporated byreference herein.

What is claimed is:
 1. An article with a field effect transistorcomprising: a substrate; and a field effect transistor disposed on thesubstrate, wherein the field effect transistor comprises an active layercomprising an amorphous oxide and a gate electrode formed so as to facethe active layer through a gate insulator, wherein the amorphous oxidecomprises an oxide comprising In—Ga—Zn—O or In—Ga—Zn—Mg—O, and whereinthe amorphous oxide comprises one type of element or a plurality ofelements selected from the group consisting of Li, Na, Mn, Ni, Pd, Cu,C, N, P, Ti, Ru and F.
 2. The article according to claim 1, wherein theamorphous oxide exhibits a halo pattern and no characteristicdiffraction line in an X-ray diffraction spectrometry.
 3. The articleaccording to claim 2, wherein the amorphous oxide has an electroncarrier concentration of less than 10¹⁸/cm³ at a temperature of 25° C.4. The article according to claim 3, wherein the amorphous oxide isobtained by using a target having a composition InGaO₃(ZnO)_(m) orInGaO₃(Zn_(1-x)MgxO)_(m) in a crystalline state where m is a naturalnumber of less than 6 and x is greater than 0 and not greater than
 1. 5.An article with a field effect transistor comprising: a substrate; and afield effect transistor disposed on the substrate, wherein the fieldeffect transistor comprises an active layer comprising an amorphousoxide and a gate electrode formed so as to face the active layer througha gate insulator, and wherein the amorphous oxide comprises an oxidecomprising In—Ga—Zn—O or In—Ga—Zn—Mg—O, and wherein the amorphous oxidecomprises one type of element or a plurality of elements selected fromthe group consisting of Li, Na, Mn, Ni, Pd, Cu, C, N, P, Ti, Ru and F ata concentration within the range of 0.1 to 3 atomic %.
 6. The articleaccording to claim 5, wherein the amorphous oxide exhibits a halopattern and no characteristic diffraction line in an X-ray diffractionspectrometry.
 7. The article according to claim 6, wherein the amorphousoxide has an electron carrier concentration of less than 10¹⁸/cm³ at atemperature of 25° C.
 8. The article according to claim 7, wherein theamorphous oxide is obtained by using a target having a compositionInGaO₃(ZnO)_(m) or InGaO₃(Zn_(1-x)Mg_(x)O)_(m) in a crystalline statewhere m is a natural number of less than 6 and x is greater than 0 andnot greater than
 1. 9. A display apparatus with a field effecttransistor comprising: a substrate; and a field effect transistordisposed on the substrate, wherein the field effect transistor comprisesan active layer comprising an amorphous oxide and a gate electrodeformed so as to face the active layer through a gate insulator, whereinthe amorphous oxide comprises an oxide comprising In—Ga—Zn—O orIn—Ga—Zn—Mg—O, and wherein the amorphous oxide comprises at least oneelement selected from the group consisting of Li, Na, Mn, Ni, Pd, Cu, C,N, P, Ti, Ru, and F.
 10. The display apparatus according to claim 9,wherein the amorphous oxide exhibits a halo pattern and nocharacteristic diffraction line in an X-ray diffraction spectrometry.11. The display apparatus according to claim 10, wherein the amorphousoxide has an electron carrier concentration of less than 10¹⁸/cm³ at atemperature of 25° C.
 12. The display apparatus according to claim 11,wherein the amorphous oxide is obtained by using a target having acomposition InGaO₃(ZnO)_(m) or InGaO₃(Zn_(1-x)Mg_(x)O)_(m) in acrystalline state where m is a natural number of less than 6 and x isgreater than 0 and not greater than
 1. 13. The display apparatusaccording to claim 9, wherein the display apparatus includes the fieldeffect transistor as switching device.
 14. The display apparatusaccording to claim 13, wherein the display is an organic EL display. 15.The display apparatus according to claim 14, wherein the display is aflexible display.
 16. The display apparatus according to claim 13,wherein the display is an LCD.
 17. A display apparatus with a fieldeffect transistor comprising: a substrate; and a field effect transistordisposed on the substrate, wherein the field effect transistor comprisesan active layer comprising an amorphous oxide and a gate electrodeformed so as to face the active layer through a gate insulator, andwherein the amorphous oxide comprises an oxide comprising In—Ga—Zn—O orIn—Ga—Zn—Mg—O, and wherein the amorphous oxide comprises at least oneelement selected from the group consisting of Li, Na, Mn, Ni, Pd, Cu, C,N, P, Ti, Ru, and F at a concentration within the range of 0.1 to 3atomic %.
 18. The display apparatus according to claim 17, wherein theamorphous oxide exhibits a halo pattern and no characteristicdiffraction line in an X-ray diffraction spectrometry.
 19. The displayapparatus according to claim 18, wherein the amorphous oxide has anelectron carrier concentration of less than 10¹⁸/cm³ at a temperature of25° C.
 20. The display apparatus according to claim 19, wherein theamorphous oxide is obtained by using a target having a compositionInGaO₃(ZnO)_(m) or InGaO₃(Zn_(1-x)Mg_(x)O)_(m) in a crystalline statewhere m is a natural number of less than 6 and x is greater than 0 andnot greater than
 1. 21. The display apparatus according to claim 17,wherein the display apparatus includes the field effect transistor asswitching device.
 22. The display apparatus according to claim 21,wherein the display is an organic EL display.
 23. The display apparatusaccording to claim 22, wherein the display is a flexible display. 24.The display apparatus according to claim 21, wherein the display is anLCD.
 25. An article with a field effect transistor comprising: asubstrate; and a field effect transistor disposed on the substrate,wherein the field effect transistor comprises an active layer comprisingan amorphous oxide and a gate electrode formed so as to face the activelayer through a gate insulator, and wherein the amorphous oxidecomprises at least In, Ga and Zn or at least In, Ga, Zn and Mg, andfurther comprises one type of element or a plurality of elementsselected from the group consisting of Li, Na, Mn, Ni, Pd, Cu, C, N, P,Ti, Ru and F.
 26. The article according to claim 25, wherein theamorphous oxide exhibits a halo pattern and no characteristicdiffraction line in an X-ray diffraction spectrometry.
 27. The articleaccording to claim 25, wherein the amorphous oxide has an electroncarrier concentration of less than 10¹⁸/cm³ at a temperature of 25° C.28. The article according to claim 25, wherein the amorphous oxide isobtained by using a target having a composition InGaO₃(ZnO)_(m) orInGaO₃(Zn_(1-x)Mg_(x)O)_(m) in a crystalline state where m is a naturalnumber of less than 6 and x is greater than 0 and not greater than 1.